Applied Surface Science 391 (2017) 72–123

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: [Link]/locate/apsusc

A review on g-C3 N4 -based photocatalysts

Jiuqing Wen a , Jun Xie a , Xiaobo Chen b,∗ , Xin Li a,∗
a
College of Materials and Energy, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture, Key Laboratory of Biomass Energy of
Guangdong Regular Higher Education Institutions, South China Agricultural University, Guangzhou, 510642, PR China
b
Department of Chemistry, University of Missouri – Kansas City, Kansas City, MO, 64110, USA

a r t i c l e i n f o a b s t r a c t

Article history: As one of the most appealing and attractive technologies, heterogeneous photocatalysis has been utilized
Received 23 May 2016 to directly harvest, convert and store renewable solar energy for producing sustainable and green solar
Received in revised form 2 July 2016 fuels and a broad range of environmental applications. Due to their unique physicochemical, optical and
Accepted 3 July 2016
electrical properties, a wide variety of g-C3 N4 -based photocatalysts have been designed to drive vari-
Available online 9 July 2016
ous reduction and oxidation reactions under light irradiation with suitable wavelengths. In this review,
we have systematically summarized the photocatalytic fundamentals of g-C3 N4 -based photocatalysts,
Keywords:
including fundamental mechanism of heterogeneous photocatalysis, advantages, challenges and the
Carbon nitride (g-C3 N4 )
Composite photocatalysts
design considerations of g-C3 N4 -based photocatalysts. The versatile properties of g-C3 N4 -based pho-
Co-catalysts tocatalysts are highlighted, including their crystal structural, surface phisicochemical, stability, optical,
Artificial photosynthesis adsorption, electrochemical, photoelectrochemical and electronic properties. Various design strategies
Z-scheme heterojunction are also thoroughly reviewed, including band-gap engineering, defect control, dimensionality tuning,
Nanocarbons pore texture tailoring, surface sensitization, heterojunction construction, co-catalyst and nanocarbon
loading. Many important applications are also addressed, such as photocatalytic water splitting (H2
evolution and overall water splitting), degradation of pollutants, carbon dioxide reduction, selective
organic transformations and disinfection. Through reviewing the important state-of-the-art advances
on this topic, it may provide new opportunities for designing and constructing highly effective g-C3 N4 -
based photocatalysts for various applications in photocatalysis and other related fields, such as solar
cell, photoelectrocatalysis, electrocatalysis, lithium battery, supercapacitor, fuel cell and separation and
purification.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction the heterogeneous photocatalysis occurring on powdered semi-

conductors has been widely used in the different fields, such
Nowadays, among the various possibilities for exploring attrac- as water splitting [6–10], environmental remediation [9,11–15],
tive sustainable energy sources and technologies, photocatalytic CO2 reduction [16–20], disinfection [21] and selective organic
technology is considered as one of the most appealing and promis- transformations[22–24]. It is noteworthy that there has been a
ing technologies to directly harvest, convert and store renewable growing interest in the use of semiconductors as photocatalysts
solar energy for generating sustainable and green energy and for various applications (the red columns in Fig. 1a). In 2015, more
a broad range of environmental applications. In 1972, the pio- than 5500 papers about the photocatalytic applications have been
neering work of photoelectrochemical (PEC) H2 production from published, further indicating the high importance and tremen-
water splitting using a Pt-attached n-TiO2 cell was firstly reported dous research interests in heterogeneous photocatalysis. Clearly,
by Fujishima and Honda [1]. Subsequently, Bard extended the the presence of efficient photocatalysts plays an essential role
basic principle of PEC water splitting system to the heteroge- in determining the overall quantum efficiency of all these pho-
neous photocatalytic systems with illuminated semiconductor tocatalytic reaction systems. During the past 40 years, various
particles suspended in water as photocatalysts [2–5]. Since then, available semiconductor materials such as TiO2 , SrTiO3 , CdS, BiVO4 ,
Ta3 N5 , TaON, g-C3 N4 , Ag3 PO4 , and their nanostructured assemblies
have been extensively employed as photocatalysts to directly har-
ness solar energy for different redox reactions [7,25–30]. As the
∗ Corresponding authors.
most widely employed “golden” photocatalyst, TiO2 has dominated
E-mail addresses: chenxiaobo@[Link] (X. Chen), Xinliscau@[Link]
the published work on heterogeneous photocatalysis owing to its
(X. Li).

[Link]
0169-4332/© 2016 Elsevier B.V. All rights reserved.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 73

Fig. 1. (a) The annual number of publications containing the word “graphene* (TiO2 *, g-C3 N4 * or carbon nitride*)” in the title and “photocataly*” in the topic since 2009. (b)
The annual number of citations for Wang’s pioneering paper published on Nature Materials in 2009. (Using Web of Science, date of search: Jul 2, 2016).

chemical stability, high chemical inertness, nontoxicity, and low ness, pore structures, size distributions, and morphologies. Hence,
cost [31–36], which accounts for three-fifths of all photocatalytic it is of great interest to develop g-C3 N4 -based photocatalysts for
research (the green columns in Fig. 1a). However, the large bandgap various applications through suitable modification, which is still
of anatase TiO2 (3.2 eV) restricts the utilization of broad spectrum considered as a research topic of scientific and technological sig-
of solar light (only utilization of the ultraviolet (UV) light in the sun- nificance in the fields of energy and environmental chemistry.
light, accounting for only 4% of the incoming solar spectrum), thus Importantly, many significant and major breakthroughs have been
leading to much lower quantum efficiencies in using the solar spec- achieved in the synthesis and application of g-C3 N4 -based photo-
tra. To enhance the photocatalytic efficiency of titania under visible catalysts. In particular, many novel nanostructured g-C3 N4 -based
light (about 43% of the sunlight), a variety of modification strategies, photocatalysts, including 1D nanorods, 2D nanosheets and 3D hier-
including doping, surface sensitization, nanostructuring, introduc- archical structures, have been extensively developed in the past
ing defects or amorphous disorder layers, loading co-catalysts, several years due to their favorable absorption of solar radia-
coupling with carbon and other semiconductors, have been utilized tion, efficient separation of charge carriers, high surface areas and
to overcome the TiO2 materials-related issues and limitations, such exposed reactive sites.
as the control of the band gap, band structure, optical properties and In fact, several excellent reviews are already available that focus
available surface area for photo-induced reactions [7,25,34–40]. on the synthesis and modification of g-C3 N4 -based photocatalysts
Up to now, no one robust and commercially available material and their applications in solving the energy and environmental
could meet all requirements, such as high visible-light quantum issues [27,45–57,59]. However, only a handful of reviews have
efficiency, stability, safety and cheapness [7,41]. Thus, to tackle focused on the versatile properties and rational design of g-C3 N4 -
these challenges, it is highly desirable to search for novel visible- based photocatalysts. Thus, it seems timely to offer a relatively
light-driven semiconductor materials and further fabricate highly comprehensive and fully updated review on the state-of-the-art
efficient systems/architectures for energy supply and environmen- advances of g-C3 N4 -based photocatalysts for heterogeneous pho-
tal remediation. tocatalysis. In the present Review, we devote our attention to
The graphite-like carbon nitride (g-C3 N4 ), as a metal-free poly- fundamentals, versatile properties, rational design and potential
mer n-type semiconductor, possess many promising properties, applications of g-C3 N4 photocatalysts. We believe that this review
such as unique electric, optical, structural and physiochemical will not only promote the further developments of new g-C3 N4 -
properties, which make g-C3 N4 -based materials a new class of based materials and architectures with improved utilization of
multifunctional nanoplatforms for electronic, catalytic and energy solar energy and photocatalytic efficiency, but also could therefore
applications [42,43]. Especially, g-C3 N4 -based photocatalysts have help to address the challenges for the widespread use of g-C3 N4 -
attracted increasing interest worldwide, since Wang and his based photocatalysts in the renewable and sustainable energy
coworkers first discovered the photocatalytic H2 and O2 evolution production and storage. It is also hoped that this review can pro-
over C3 N4 in 2009 [44]. Clearly, the annual number of citations for vide some new ideas to develop new materials and architectures
Wang’s pioneering paper published on Nature Materials in 2009 for the other sustainable energy-related fields such as solar cells
significantly increases every year (as shown in Fig. 1b). Thus, the [42,43,60,61], light emitting devices [62,63], fuel cells [64–69], bat-
g-C3 N4 -based nanostructures are emerging as ideal candidates for teries [70–75] and sensing devices [76–82].
a variety of energy and environmental photocatalytic applications,
such as photocatalytic water reduction and oxidation, degradation
of pollutants and carbon dioxide reduction [27,45–57]. More inter- 2. Fundamentals of g-C3 N4 -based photocatalysts
estingly, as observed from Fig. 1b, although the annual number of
publications about g-C3 N4 -based photocatalysts is much smaller 2.1. Mechanism of heterogeneous photocatalysis
than that about TiO2 photocatalysts, the publications of g-C3 N4
photocatalysis present an obvious approach to those of graphene- So far, the fundamental mechanism of heterogeneous photo-
based photocatalysis [26,58]. More interestingly, the g-C3 N4 -based catalysis has been well proposed, as shown in Fig. 2. Basically
photocatalysts together with the graphene-based ones are signif- speaking, the heterogeneous photocatalysis involves seven key
icantly reducing the proportion of TiO2 photocatalysts (as shown stages, which could be usually classified into four major processes:
in Fig. 1a). Absolutely, the g-C3 N4 , as the very exciting sustainable light harvesting (stage 1); charge excitation (stage 2); charge sep-
material, has become a shining star in the photocatalytic field. aration and transfer (stages 3, 4 and 5) and surface electrocatalytic
Interestingly, as a novel metal-free polymeric semiconductor, g- reactions (stages 6 and 7). Firstly, it is known that the light har-
C3 N4 was quite different from most other semiconductors, which vesting process (stage 1) is strongly dependent on the surface
could also be readily utilized to form various highly tailorable morphology and structure of photocatalysts, which can usually
hybrid photocatalysts with controllable compositions, sizes, thick- be significantly improved through constructing the hierarchical
macroporous or mesoporous architectures, due to more efficient
74 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Table 1
Band gap structures of several typical photocatalysts.

Semiconductor Crystal structure Band Gap Structure (PH = 7,vs NHE) Ref.

CB VB Eg /eV

TiO2 Anatase −0.5 2.7 3.2 [90]

Cu2 O −1.16 0.85 2.0 [91]
CdS −0.9 1. 5 2.4 [92]
g-C3 N4 −1.3 1.4 2.7 [44,84]
g-C3 N4 −1.53 1.16 2.7 [93]a
Ta3 N5 −0.75 1.35 2.1 [94]
TaON −0.75 1.75 2.5 [94]
BiVO4 −0.3 2.1 2.4 [95]
WO3 −0.1 2.7 2.8 [96]
Ag3 PO4 cubic 0.04 2.49 2.45 [97]
a
Measurement by the valence band X-ray photoelectron spectroscopy (VB XPS) spectrum.

Table 2
Standard redox potentials for some typical species [83,98].

Reaction E0 (V) vs NHE at pH 0

2H+ + 2e− →H2 (g) 0

O2 (g) + e− →O2 − (aq) −0.33
O2 (g) + H+ + e− → HO2 • (aq) −0.046
O2 (g) + 2H+ + 2e− → H2 O2 (aq) 0.695
2H2 O (aq) + 4 h+ → O2 (g) + 4H + 1.229
OH− + h+ → • OH 2.69
O3 (g) + 2 H+ + 2 e− → O2 (g) + H2 O 2.075
CO2 + e− →CO2 − −1.9
2 CO2 (g) + 2 H+ + 2 e− → HOOCCOOH(aq) −0.481
CO2 (g) + 2H+ + 2e− → HCOOH(aq) −0.199
CO2 (g) + 2 H+ + 2e− → CO(g) + H2 O −0.11
CO2 (g) + 4H+ + 4e− → C(s) + 2H2 O 0.206
CO2 (g) + 4H+ + 4e− → HCHO(aq) + H2 O −0.07
CO2 (g) + 6H+ + 6e− → CH3 OH(aq) + H2 O 0.03
CO2 (g) + 8H+ + 8e− → CH4 (g) + 2H2 O 0.169
2CO2 (g) + 8H2 O + 12e− → C2 H4 (g) + 12OH− 0.07
2CO2 (g) + 9H2 O + 12e− → C2 H5 OH(aq) + 12OH− 0.08
3CO2 (g) + 13H2 O + 18e− → C3 H7 OH(aq) + 18OH− 0.09
H2 O2 (aq) + H+ + e− → H2 O + OH− 1.14
HO2 • + H+ + e− → H2 O2 (aq) 1.44
Fig. 2. The fundamental mechanism of heterogeneous photocatalysis. The typical H2 O2 (aq) + 2H+ + 2e− → 2H2 O 1.763
stages: (1) light harvesting; (2) charge excitation; (3) charge separation and trans-
fer; (4) bulk charge recombination; (5) surface charge recombination; (6) surface
reduction reactions; and (7) surface oxidation reactions.
surface active sites or co-catalysts, and further stimulate the elctro-
catalytic reduction (stage 6) and oxidation (stage 7) reactions of the
utilization of light through its multiple reflections and scattering reactants adsorbed on the semiconductor, respectively. It should
effects [83]. At this regard, the flat and smooth surface of 2D g- be noted that the surface reactions possibly occur only when the
C3 N4 is unfavorable for improving the light harvesting. Secondly, reduction and oxidation potentials are more positive and negative
the charge excitation of a semiconductor is strongly associated than CB and VB levels, respectively. Some typical standard redox
with its unique electronic structures. Generally, an electron in the potentials have been listed in Table 2. Notably, almost all reac-
VB of the semiconductor could be thus excited to its CB under tions in Table 2 exhibit the same linear pH dependence with a
the light irradiation with energy higher than or equal to its band slope of −0.059 V, apart from E0 (O2 /O2 − ) which is pH-independent
gap energy (Eg ), leaving a positive hole in the VB. The band gap [83,87]. Furthermore, for the surface electrocatalytic reactions (sur-
structures of several typical photocatalysts were summarized in face charge utilization), the large onset overpotential and sluggish
Table 1. As observed in Table 1, as compared to TiO2 , BiVO4 and kinetics are two key factors limiting the surface photocatalytic
WO3 , g-C3 N4 has the most negative CB level (−1.3 V vs NHE at pH efficiency of reduction and oxidation reactions. Principally, these
7) and a medium band gap (2.7 eV) [44,84], facilitating its wide two restrictive factors can be overcome by loading suitable co-
application in visible-light photocatalysis. Thus, to achieve more catalysts (electrocatalysts) simultaneously [88]. More importantly,
utilization of visible light, the band gap of g-C3 N4 should be further the co-catalysts (electro-catalysts) can play the additional roles in
narrowed by facile doping, defect and other possible sensitization improving the photostability and charge separation of semicon-
strategies [7]. Thirdly, the unfavorable charge recombination in ductors [89]. The complicated co-catalyst effects will be thoroughly
the bulk (stage 4) and on the surface (stage 5) of a semiconduc- discussed in the section 4.7.
tor is detrimental to the charge separation and transfer (stage 3) to However, it should be noteworthy that the photocatalytic quan-
surface/interface active sites, which has been regarded as the deci- tum efficiency (c ) is strongly determined by the cumulative effect
sive factor for determining the photocatalytic quantum efficiency. of the efficiency in all four-step processes, including light har-
Usually, shortening the diffusion length of photo-generated charge vesting efficiency (abs ), charge separation efficiency (cs ), charge
carriers or constructing interfacial electric fields could efficiently migration and transport efficiency (cmt ), and charge utilization
reduce the recombination rates, thus substantially enhancing the efficiency (cu ) for H2 generation. The relationship between them
photocatalytic activity [7,85,86]. Finally, it is clear that only ener- could be expressed according to Eq. (1) [7]:
getic enough electrons and holes that migrate to the surface of
the semiconductor without recombination can be trapped by the c = abs × cs × cmt × cu (1)
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 75

Fig. 3. The redox potentials of the relevant reactions with respect to the estimated position of the g-C3 N4 band edges at pH 7.

Therefore, to design highly efficient photocatalysts for various

photocatalytic applications, all these typical four-step processes
must be comprehensively considered and optimized. Despite the
significant advances in heterogeneous photocatalysis, there are
still many challenges related to the further enhancements of
light harvesting (especially for the visible light region), charge
carrier excitation, separation and utilization. In order to solve
these key scientific problems, a variety of engineering modifi-
cation strategies have been proposed and applied in improving
the visible-light photocatalytic performances of heterogeneous
semiconductor materials, such as band structure engineering,
micro/nano engineering, bionic engineering, co-catalyst engineer-
ing, surface/interface engineering and their synergistic effects [7].
The detailed modification strategies and rational design on g-C3 N4 -
based photocatalysts will be thoroughly discussed in section 4.

2.2. Advantages and challenges of g-C3 N4 -based photocatalysts

Based on the above mechanism analysis, it is clear that the Fig. 4. Fabrication strategies of g-C3 N4 and N-rich precursors.
band-gap and nano structures are crucial for their photocatalytic
applications. The band gap structures of g-C3 N4 , as well as some
standard potentials of typical redox reactions at pH 7 are illustrated of 0.75, suggesting that g-C3 N4 could be readily fabricated at low
in Fig. 3. Clearly, as shown in Fig. 3, g-C3 N4 has a moderate band cost. It also turned out that the g-C3 N4 has the advantages of bio-
gap of 2.7 eV, corresponding to an optical wavelength of 460 nm, compatibility and nontoxicity. Surprisingly, the viability activity
which makes it active under visible light. Considering thermody- of HeLa cells could be maintained in the aqueous solution of g-
namic losses and overpotentials in the photocatalytic process, the C3 N4 nanosheets with a concentration of up to 600 mg mL−1 [100].
band gap of 2.7 eV accidentally lies in between 2 eV and 3.1 eV, Furthermore, g-C3 N4 could be readily fabricated through the tra-
thus achieving both the water-splitting with enough endother- ditional thermal condensation of several low-cost N-rich organic
mic driving forces (much larger than 1.23 eV) and light absorption solid precursors such as urea, thiourea, melamine, dicyandiamide,
in the visible range (smaller than 3.1 eV) [7]. More importantly, cyanamide, and guanidine hydrochlorid, at 500–600 ◦ C in air or
g-C3 N4 also has a suitable CB position for various reduction reac- inert atmosphere (Fig. 4) [27,101]. However, the disordered and
tions. It is noted form Fig. 3 that the favorable level of top CB of defective g-C3 N4 structures could be fabricated due to the incom-
g-C3 N4 is much more negative than those of conventional inor- plete removal of intermediates. Thus, the crystalline and condensed
ganic semiconductor counterparts in Table 1 and the potentials g-C3 N4 can be readily prepared by other various fabrication strate-
of H2 -evolution, CO2 -reduction and O2 -reduction reactions, sug- gies, including the ionothermal synthesis (molten salt strategy)
gesting that the photo-generated electrons in g-C3 N4 possess a [102–106], molecular self-assembly [107–111], microwave irradi-
large thermodynamic driving force to reduce various kinds of small ation [112,113] and ionic liquid strategy [114–117] (Fig. 4).
molecules, like H2 O, CO2 and O2 . As a consequence, the appropriate In addition, the above three obvious advantages, as well as
electronic band structures of g-C3 N4 are favorable for its extensive several other advantages of g-C3 N4 , including the rich surface
applications in wide areas, such as photocatalytic water splitting, properties, non-toxicity, abundance, and good stabilities, are sum-
CO2 reduction, pollutant degradation, organic synthesis and disin- marized in Fig. 3, all of which give access to a wide variety of
fection. applications [48]. All these features principally already allow its
Apart from the simplest and straightforward advantage of suit- direct use in sustainable chemistry as a multifunctional heteroge-
able optical band gap and position, it is widely accepted to date neous metal-free photocatalyst.
that this metal-free g-C3 N4 material also possesses a stacked 2D Unfortunately, the bulk g-C3 N4 generally exhibits the low pho-
layered structure, in which the single-layer nitrogen heteroatom- tocatalytic efficiency, due to some serious drawbacks of g-C3 N4
substituted graphite nanosheets, formed through sp2 hybridization material itself. Specifically, we will highlight several prominent
of C and N atoms, are bound by van der Waals forces, only (as challenges of g-C3 N4 itself here: the high electron–hole recom-
shown in Fig. 4a) [99]. Ideally, condensed g-C3 N4 consists of only bination rate, insufficient visible absorption (below 460 nm), low
two earth-abundant elements: C and N, with a C/N molar ratio surface area of g-C3 N4 (∼10 m2 /g, the high degree of conden-
76 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Table 3
Structural parameters and total energies for different C3 N4 phases [131].

C3 N4 phases Space group Lattice parameter (Å) Z GW approximation band gap (eV) local density approximation band gap (eV)

Alpha P31 c (159) a = 6.465, c = 4.709 4 5.49 3.76

Beta P3 (143) a = 6.406, c = 2.406 2 4.85 3.12
Cubic I-43d (220) a = 5.411 2 4.30 2.87
Pseudocubic P–42 m (111) a = 3.426 1 4.13 2.53
g-h-triazine P-6m2 (187) a = 4.746, c = 6.586 2 2.97 1.16
g-h-heptazine Cmc21 (36) a = 7.083, b = 12.269, c = 6.871 4 2.88 0.89
g-o-triazine P2 mm (25) a = 4.147, b = 4.754, c = 6.474 2 0.93 –

composition, structures and properties. More definitely speak-

ing, hetero-junction construction [120,121], dimensionality tuning
(nano-templating [122,123]) and nanocarbon loading have been
widely applied in promoting the charge transfer, mobility and
separation respectively. Furthermore, suitable co-catalyst loading
[44,124–127] and defect control have been available in accelerating
the surface reaction kinetics (charge utilization). In addition, pore
texture tailoring, surface sensitization, and band-gap engineer-
ing (non-metal doping [128] and co-polymerization [84,129,130]
strategies) were utilized to create highly mesoporous g-C3 N4 with
high surface area and to increase the light harvesting and visi-
ble absorption through the red-shift of its optical absorption edge,
respectively. In future, it is expected more and more engineering
modification strategies will be developed to improve the pho-
tocatalytic performances of g-C3 N4 -based photocatalysts. More
importantly, all different photocatalytic stages such as light har-
vesting, charge excitation, charge transfer, mobility and separation,
and surface charge utilization should be simultaneously consid-
ered and optimized [7]. In other words, the synergy and integration
effect of these different strategies should be paid more attention.
In the following sections, the versatile properties, design strategies
and potential applications will be thoroughly summarized.

Fig. 5. Design considerations of g-C3 N4 -based photocatalysts based on the different 3. Versatile properties of g-C3 N4 -based photocatalysts
photocatalytic stages.

As is known, the photocatalytic efficiency of g-C3 N4 -based pho-

sation of the monomers) and small active sites for interfacial tocatalysts is mainly governed by all parameters/properties of
(photo)reactions, slow surface reaction kinetics, moderate oxida- g-C3 N4 itself, including crystal structural, surface physicochemical,
tion ability, grain boundary effects and low charge mobility which stability, optical, adsorption, electrochemical, photoelectrochemi-
disrupt the delocalization of electrons [51,118]. Additionally, it cal and electronic properties. Thus, a fundamental understanding
should be noted from Fig. 3 that the photo-generated holes of and deterministic control of these chemical and structural factors
C3 N4 with moderate oxidation ability can only achieve oxygen will enable the scalable production of g-C3 N4 -based composite
evolution from water oxidation, instead of the formation of the non- photocatalysts with the best photocatalytic behavior, which will be
selective hydroxyl radicals, • OH. At this point, the g-C3 N4 -based favorable for creating some robust g-C3 N4 -based material systems
photocatalysts seem to be a suitable candidate for selective pho- for practical photocatalytic applications and fundamental insights
tooxidation and related transformations of organic compounds in into photocatalytic enhancement mechanisms at the single-atom
aqueous media, avoiding the direct mineralization to CO2 by the level.
strong • OH [119]. Thus, it is therefore highly desirable to lower
the top level of VB of C3 N4 to enhance its water oxidation power, 3.1. Crystal structural properties
as 4-electron water oxidation reaction oxidation to O2 is a more
challenge half-reaction for water splitting. Although these promi- It is known that C3 N4 possesses seven different phases, e.g.,
nent challenges of g-C3 N4 itself greatly limit its photocatalytic ␣-C3 N4 , ␤-C3 N4 , cubic C3 N4 , pseudocubic C3 N4 , g-h-triazine, g-h-
performance enhancements, they also afford more opportunities to heptazine and g-o-triazine, which exhibit the band gaps of 5.49,
construct more efficient g-C3 N4 -based photocatalysts in the future 4.85, 4.30, 4.13, 2.97, 2.88 and 0.93 eV, respectively, in terms of GW
studies. method (as shown in Table 3) [131]. Among them, the famous super
hard ␤-C3 N4 crystalline phase has been demonstrated to possess
2.3. Design considerations of g-C3 N4 -based photocatalysts the similar hardness/low compressibility to that of diamond [132].
Except the pseudocubic and g-h-triazine phases, other five phases
For these above reasons, careful consideration must be given have indirect band gaps in their bulk structures [127,131,133].
to the rational design of g-C3 N4 for achieving the optimum As observed from Table 3, it is clear that g-h-triazine and g-h-
photocatalytic performances. To avoid some of these drawbacks heptazine phases exhibit the suitable band gaps of 2.97 and 2.88 eV
and maximize the photocatalytic efficiency, several modifica- for visible-light absorption, favoring their applications in differ-
tion strategies have been pursued to design highly efficient ent photocatalytic fields. More interestingly, g-C3 N4 also shows
g-C3 N4 -based photocatalysts. Fig. 5 summarizes the design con- the stacked 2D layered structure, as displayed in Fig. 6a. Further-
siderations of g-C3 N4 -based photocatalysts based on their detailed more, two different condensation states have been demonstrated
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 77

Fig. 6. The stacked 2D layered structure of g-C3 N4 (a); structures of s-triazine (b) and tri-s-triazine (c) as the primary building blocks of g-C3 N4 .

Fig. 8. Multiple functional surface properties of polymeric g-C3 N4 material with

Fig. 7. XRD patterns of (a) the tubular carbon nitride and (b) the bulky g-C3 N4 defects [101].
synthesized by directly heating melamine at 520 ◦ C for 2 h [138].

of g-C3 N4 could be readily identified by the XRD peak associated

as the primary building block in a single layer of g-C3 N4 networks: with an in-plane structural packing motif.
s-triazine units (ring of C3 N3 ; Fig. 6b) with a periodic array of single
carbon vacancies; and tri-s-triazine/heptazine subunits (triring of 3.2. Surface physicochemical properties
C6 N7 ; Fig. 6c) connected through planar tertiary amino groups with
larger periodic vacancies in the lattice [134]. More importantly, it It is known that a variety of surface defects on the surface of
has been experimentally and theoretically demonstrated that the polymeric g-C3 N4 material lead to the formation of multiple func-
energetically favored tri-s-triazine-based g-C3 N4 was 30 kJ mol−1 tionalities. Commonly, the basic primary and/or secondary amine
more stable than the triazine-based g-C3 N4 , adequately suggest- groups (e.g., CNH2 and C2 NH) on the terminating edges in the
ing that tri-s-triazine is the most widely accepted basic unit for the single layer of g-C3 N4 (as shown in Fig. 8) could be created by
g-C3 N4 networks [131,134–136]. a small quantity of hydrogen impurity, owing to the incomplete
It is known that XRD has been extensively employed to pre- polycondensation [49,101]. Therefore, it is not surprising that the
cisely measure the lattice constant and crystal structures. The g-C3 N4 materials with surface defects and electron-rich properties
typical experimental XRD pattern of bulky g-C3 N4 powders have also exhibit the unique nucleophilic character from basic surface
two distinct diffraction peaks located at 27.40◦ and 13.0◦ (as shown functionalities (for the activation of CO2 ) or H-bonding motifs (as
in Fig. 7b), which can be indexed as (002) and (100) diffraction shown in Fig. 8), thus facilitating their more valuable applications
planes for graphitic materials (JCPDS 87-1526) [44]. Clearly, the in catalysis, as compared to the ideal and defect-free g-C3 N4 [101].
XRD results indicate that the g-C3 N4 exhibits the flake-like struc- Furthermore, it is easily understood that the abundant basic groups
ture with interplanar stacking distance of 0.325 nm revealed by ( NH , N , NH2 and N C ) on the surface of g-C3 N4 are ben-
(002) diffraction, which is similar to that of graphite with stacking eficial for the removal of acidic toxic molecules through chemical
distance of 0.34 nm [102,137]. The distance of 0.681 nm for in-plane adsorption based on electrostatic interactions [139]. Similar to the
structural packing motif is slightly smaller than that of the tris-s- hydrophobic nature of the nanocarbon surface, hydrophobicity of
triazine units (ca. 0.73 nm), presumably due to the bending of 2D g-C3 N4 could lead to the formation of weakly interacted interfacial
layered structures [44]. However, the g-C3 N4 nanotubes exhibit one layer, thus significantly restricting the electron transport and sepa-
distinct XRD diffraction peak at 17.4◦ (corresponding to an interpla- ration and surface electrocatalytic reactions [61]. At this point, the
nar separation of d = 0.49 nm, Fig. 7a), indicating the formation of hydrophilicity of g-C3 N4 materials (with decreasing contact angle
the s-triazine units (with the theoretical value of d = 0.47 nm [127]) of water on their surface) could be improved through introducing
in g-C3 N4 [138]. Consequently, the exact periodic units in each layer oxygen-containing functional groups (hydroxyl and carboxyl) by
78 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

peaks observed in the region from 900 to 1700 cm−1 were usually
assigned to stretching vibration signals of aromatic heptazine-
derived repeating units, including the typical sp2 C N stretching
modes and out-of-plane bending vibrations of the sp3 C N
bonds [130,147–150], while the sharp absorption peak centered
at approximately 810 cm−1 was attributed to the characteristic
breathing mode of tri-s-triazine cycles [150–152]. Meanwhile, the
absorption band at 883 cm−1 were indexed as the deformation
mode of N H in amino groups [153], whereas the broadened
peaks between 3000 and 3500 cm−1 were related to the stretch-
ing vibration [146,149,150,153] of residual free N H in the bridging
C NH C units and O H originated from physically adsorbed water
species on g-C3 N4 surface, respectively. In the recorded Raman
spectra, several characteristic peaks of g-C3 N4 can be observed
at 1616, 1555, 1481, 1234, 751, 705, 543, and 479 cm−1 , further
confirming the vibration modes of CN heterocycles [151,154]. It
should be noted that the peak at 1234 cm−1 , corresponding to
Fig. 10. Comparison between the Raman spectra of coplanar bulk and 1-layer g- the N C (sp2 ) bending vibration, exhibits significant blue shift
C3 N4 samples (780 nm laser) [154]. (1250 cm−1 for 1-layer g-C3 N4 ), due to the phonon confinement
and strong quantum confinement effect [154]. Moreover, it has also
been experimentally and theoretically demonstrated that the ratios
of peak heights of 751–705 cm−1 (I751 /I705 ) and 543–479 cm−1
(I543 /I479 ), corresponding to layer–layer deformation vibrations or
the correlation vibrations, obviously increased with decreasing the
layer number of g-C3 N4 [154]. Additionally, the nitrogen contain-
ing species can be further quantitatively analyzed by the element
analysis and Boehm titration. For the element analysis, X-ray pho-
toelectron spectroscopy (XPS) can not only reveal the atom ratio
of carbon to nitrogen, but also identify the carbon and nitrogen
species in g-C3 N4 . For example, the main peak at 288.2 eV in the
high-resolution C 1s XPS spectra of the 1.0 wt% RGO/g-C3 N4 sam-
ple, indicates the existence of the N C N2 coordination [151]. The
N 1 s binding energies at about 398.6, 399.8, and 401.5 eV in the
high-resolutionN1 s XPS spectra of the 1.0 wt% RGO/g-C3 N4 sam-
ple can be assigned to sp2 -hybridized nitrogen (C N C), tertiary
nitrogen (N (C)3 ) and amino functional groups having a hydrogen
Fig. 9. FTIR spectra of g-C3 N4 powders obtained by heating melamine (MCN),
atom (C N H), respectively [146,151,155,156]. For Boehm titra-
thiourea (TCN), and urea (UCN) [146]. tion analysis, it was found that the content of basic group per unit
area of g-C3 N4 generally decreased with increasing the calcination
temperature [157]. In a word, the combination of Raman vibra-
means of chemical oxidation, thus greatly favoring their good dis-
tion properties, FTIR, XPS spectra and Boehm titration analysis can
persion in the aqueous solutions and further enhanced interfacial
fully reveal the surface functional groups of g-C3 N4 nanomaterials
coupling and photocatalytic activities [140–145].
(Figs. 9,10 and 11).
Commonly, these functional groups and networks (C N ) could
Interestingly, the basic surface functionalities can be further
be further identified by the Fourier transform infrared (FT-IR) spec-
evidenced by the isoelectric point (IEP) and the zeta potentials of
tra, X-ray photoelectron spectroscopy (XPS) measurements, Raman
g-C3 N4 dispersions [146]. It is known that the IEP is an important
spectra, and Boehm titration analysis. Generally, the chemical com-
physicochemical parameter of many compounds, such as oxides,
position and bonding information of g-C3 N4 could be partially
sulfides, hydroxides, and nitrides, which has been widely used
identified by FT-IR measurement. Fig. 9 depicts typical FTIR spectra
to estimate the surface charges of compound particles at vari-
of g-C3 N4 powders obtained by heating melamine (MCN), thiourea
ous pH conditions. In general, the solid particles are positively
(TCN), and urea (UCN) [146]. As shown, the main characteristic

Fig. 11. High-resolution XPS spectra of C 1s (A) for the 1.0 wt% RGO/g-C3 N4 sample (a) and GO (b) and N 1s (B) for the 1.0 wt% RGO/g-C3 N4 sample [151].
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 79

ther oxidation decomposition (630–750 ◦ C) of g-C3 N4 material

[44,149]. It has been observed that melem transforms into a g-C3 N4
material by temperature-dependent X-ray powder diffractometry
investigations above 560 ◦ C [134]. The complete decomposition
temperature of g-C3 N4 ranging from 700 to 750 ◦ C, is in good
agreement with the Gillan’s report [167,170]. These typical pro-
cesses were also observed during the formation of g-C3 N4 by using
cyanamide as precursors (as shown in Fig. 14), except for the first
formation of melamine through condensing the cyanamide pre-
cursors [101]. Notably, the thermal stability of g-C3 N4 has been
regarded to be the highest in organic materials, which can be
obviously affected by the different polymerization degrees of g-
C3 N4 in different preparation methods [149,167,170–173]. The
high thermal stability of g-C3 N4 polymeric semiconductor not only
features its various applications, as a heterogeneous organic cata-
lyst, at operating temperature below 500 ◦ C, but also allows its easy
Fig. 12. Zeta potentials of MCN, TCN, and UCN powders as functions of the pH value
removal by simply increasing the calcination temperature beyond
of the suspensions (as shown in Fig. 12) [146]. 600 ◦ C, thus favoring its utilization as confinement templates, struc-
turing agents or nitrogen sources for synthesizing a refined carbon
nanostructure or metal nitride nanostructures with continuously
charged and negatively charged at pH values below and above the adjustable composition, such as TaON, Ta3 N5 , ternary aluminum
IEP point, respectively. For example, Wang et al. found that the gallium nitride and titanium vanadium nitride [55,174–177].
zeta-potential of bulk g-C3 N4 dispersions in water was −47.4 mV, Furthermore, the g-C3 N4 also exhibits superior chemical stabil-
showing a negative surface charge, whereas, g-C3 N4 exhibited a ity [167]. Similar to that of graphite, it has been demonstrated that
positive surface charge with a zeta-potential of +30 mV after the the g-C3 N4 with optimized van der Waals interactions between
successful protonation in HCl solution [158]. Similarly, Yu and his the single layers is insoluble in water, acid, base, and various
coworkers experimentally demonstrated that the IEPs of TCN, MCN, kinds of organic solvents, including ethanol, toluene, diethyl ether
and UCN samples are 4.4, 5.0 and 5.1, respectively, further con- and THF [55,127,133,167]. However, notably, the molten alkali
firming their basic and negatively charged surface. Thus, in the metal hydroxides and KMnO4 could lead to the hydroxolysis and
initial pH, the MCN, UCN and TCN samples exhibited the nega- the strong oxidation decomposition of intrinsic structures of the
tive Zeta potentials of −17.0, −30.7 and −19.9 mV, respectively (as g-C3 N4 materials, respectively [178]. In particular, the excellent
shown in Fig. 12) [146]. Thus, the surface protonation of g-C3 N4 acid stability and interesting protonation effects have been also
treated by the acid solution with pH below its IEPs has become a further confirmed [178]. Commonly, the concentrated-acid treat-
popular strategy to reverse the surface properties of g-C3 N4 from ment at room temperature could result in the formation of a
negative to positive charge, facilitating the construction of com- non-transparent solution containing highly dispersed nanosheets
posite materials through electrostatic interactions with negatively without destroying the graphite-like structure of g-C3 N4 [158],
charged materials and the enormous enhancement in photocat- because the protonation effects could break both sheets and stacks
alytic performance [138,158–162]. It was believed that surface from its defects, as well as fabricate a highly porous texture
protonation modification could simultaneously achieve better dis- between the adjoining layers. Zhang et al. demonstrated that the
persion, adjusted electronic band gaps, and increased surface area relatively good-quality g-C3 N4 thin films could be fabricated by
and ionic conductivity [158]. In the contrary, the surface modifica- conventional dip/disperse-coating techniques using a stable pro-
tion of g-C3 N4 via alkaline hydrothermal treatment (e.g. NaOH and tonated g-C3 N4 colloidal suspension [179]. More recently, the first
ammonium hydroxide) can create more surface hydroxylation and liquid state NMR spectra and a lyotropic liquid crystal phase of
rich surface H-bond network of g-C3 N4 with the negatively charged g-C3 N4 have been successfully observed through the highly pro-
surface, thus greatly enhancing the interfacial charge transfer, and tonated g-C3 N4 thermodynamic solutions with concentration up
increasing the specific surface area and pore volume [163–165]. to 300 mg mL−1 , highlighting the promising applications of g-C3 N4
Particularly, the H-bonding network can offer multiple channels solubilization technique in concentrated H2 SO4 [180].
and inmate interfaces for the proton transfer from water to the
photo-excited electrons on g-C3 N4 surface, stabilize the negatively 3.4. Electronic properties
charged intermediate and transition states, thus obviously promot-
ing charge separation and photocatalytic H2 evolution [166]. It is well known that the suitable electronic properties play
important roles in better photocatalysis. To look insight into
3.3. Stability properties its electronic structure, the density-functional-theory (DFT) cal-
culations were applied in obtaining the detailed oxidation and
The defect-rich and N-bridged tri-s-triazine-based g-C3 N4 was reduction levels of valance and conduction bands. The results
found to be energetically favored relative to the other phases, shown in Fig. 15 demonstrated that the highest occupied molec-
which exhibits extraordinary thermal stability up to 600 ◦ C ular orbital/lowest unoccupied molecular orbital (HOMO-LUMO)
[149,167–169]. In air, over a period of months, the stable g-C3 N4 gaps of melem molecule, polymeric melon and an infinite sheet of
only exhibited a slightly lighter color change, because of its strong a hypothetically, fully condensed g-C3 N4 were 3.5, 2.6 and 2.1 eV,
water adsorption effects [167]. Fig. 13 gives the thermogravimetric- respectively [44]. Clearly, the calculated band gap of polymeric
differential scanning calorimetry (TG-DSC) analysis for melamine melon is very close to the experimentally measured medium-band
and g-C3 N4 prepared by heat polymerization of melamine at gap of 2.7 eV. The wavefunction investigations of the valence band
520 ◦ C in air [149], which clearly indicated that the formation and (Fig. 15b) and conduction band (Fig. 15c) are mainly derived from
decomposition of g-C3 N4 (stable up to 600 ◦ C) involve a series nitrogen pz orbitals and carbon pz orbitals, which serve as oxidation
of processes, e.g., the sublimation and thermal condensation of and reduction sites for O2 and H2 evolution reactions, respectively
melamine (297–390 ◦ C), de-ammonation process (545 ◦ C) and fur- [44]. Recently, it was found that, compared to the underestimated
80 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 13. The TG-DSC analysis for heating the melamine (a) and the g-C3 N4 (b) obtained by heat polymerization of melamine at 520 ◦ C [149].

Fig. 14. Reaction path for the formation of g-C3 N4 starting from cyanamide.

band gaps of semiconductors and insulators calculated by density

functional theory (DFT) with local density approximation (LDA),
the band structures obtained by the GW approximation (larger
than the LDA band gap by 1.73 eV) are much more close to the
experimentally reported values [131].
Besides the DFT calculations, the band edge positions of g-C3 N4
materials can be determined by electrochemicalimpedance spec-
tra (EIS), based on the Mott–Schottky (M–S) plot, and the valence
band X-ray photoelectron spectra (VB-XPS), respectively [7]. Wang
and his coworkers measured the flat band potentials of bulk g-
C3 N4 through the M–S method, indicating that its conduction band
and valance band edges are located at −1.3 and 1.4 V vs NHE at
pH 7, respectively [54,84,187]. Meanwhile, Yan et al. obtained the
accurate conduction band and valance band edges of bulk g-C3 N4
located at −1.53 and 1.16 V vs NHE at pH 7 by the VB-XPS mehod,
respectively [93]. However, it is worthy of noting that these two
results seem to be slightly contradictory. The main reason is prob-
ably that many researchers directly equate the flat-band potential
with the conduction band potential. In fact, for an n-type semi-
conductor, the conduction band potential is more negative by
about −0.1 or −0.2 V than the flat-band potential [7]. Consider-
ing the slight difference (−0.2 V) between the flat-band potential
and the conduction band potential, there was complete agreement
between these two experimental results. The band structures of
Fig. 15. Electronic structure of g-C3 N4 . (a) DFT band structure for g-C3 N4 calculated
different types of g-C3 N4 samples obtained by these two methods
along the –X and Y– directions. The potentials for H+ to H2 and H2 O to O2 are have been summarized and listed in Fig. 16. As shown in Fig. 16, the
displayed by the blue and red dashed lines, respectively; the Kohn–Sham orbitals doping of P and C can make the conduction and valance band edges
for the valence band (b) and conduction band (c) of g-C3 N4 . The C, N and H atoms are of g-C3 N4 more negative and positive, respectively, thereby facili-
gray, blue and white, respectively. The isodensity surfaces are drawn for a charge
tating the reduction and oxidation reactions. In future, it is expected
density of 0.01qe ◦ A−3 [44]. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.) that more accurate band positions of g-C3 N4 could be available and
applied in the design and development of highly efficient g-C3 N4 -
based photocatalysts.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 81

Fig. 16. Schematic illustration of the band structures of different types of g-C3 N4 samples: g-C3 N4 [84], Fe–g-C3 N4 [54,181], S–g-C3 N4 [182], P–g-C3 N4 [183], O–g-C3 N4 [184],
C–g-C3 N4 [185], I–g-C3 N4 [186] and B–g-C3 N4 [84]. VB-XPS: valence band X-ray photoelectron spectroscopy; MS: electrochemical analysis by Mott–Schottky plots.

Fig. 17. (a), time-resolved PL spectrum monitored at 525 nm under 420 nm excitation at 298 K for bulk g-C3 N4 (black) and mpg-C3 N4 (red) [123];(b), time-resolved PL spectra
monitored at 480 nm under 420 nm excitation at 77 K for CN and CNS–CN [121]. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)

In addition, the underlying electronic properties and charge car-

rier dynamics, including the microscopic dynamic process of the
charge generation, recombination, separation, and transfer, play
crucial roles in determining the photocatalytic performance [7,58].
Thus, the in-depth understanding of the electrical properties and
charge carrier dynamics is, therefore, fundamentally important
to help us to design and construct the more efficient and stable
g-C3 N4 -based composite photocatalysts. To date, many different
advanced techniques, such as femtosecond transient absorption
(TA) spectroscopy [188,189], time-resolved fluorescence spec-
troscopy, transient photocurrent decay, Nyquist impedance plots
and the transient photovoltage (TPV) technique [190–195] have
been available in studying the charge carrier dynamics of g-C3 N4 -
based composite photocatalysts. For instance, Wang et. al measured
the time-resolved PL spectrum of bulk g-C3 N4 and revealed that the
photoinduced charge carriers in bulk g-C3 N4 showed a lifetime of
∼5 ns even at 298 K, indicating the fast recombination rate (Fig. 17a)
[123]. The greatly suppressed PL signal of mpg-C3 N4 further indi- Fig. 18. SPV of g-C3 N4 (Ni0) and Ni@g-C3 N4 (Ni10). The inset shows the schematic
cated that the surface terminal sites of mpg-C3 N4 can promote the setup of SPV measurements [192].
electron relocalization, thus accelerating the catalytic functions of
mpg-C3 N4 for surface redox reactions. Similarly, the isotype hetero-
junctions between g-C3 N4 and S-doped g-C3 N4 have been found to of 300–450 nm could be achieved through loading Ni nanoparti-
exhibit a matched band alignment, which can significantly promote cles on g-C3 N4 as co-catalysts, suggesting the greatly accelerated
the charge separation between them, thus resulting in prolonging charge separation efficiency [192,193].
the lifetime of photo-excited charge carriers by about 2.15 ns [121].
It is believed that the prolonged lifetime of photo-generated charge 3.5. Optical properties
carriers could further increase their utilization efficiency in driving
surface photoredox reactions. Recently, the TA spectra of g-C3 N4 For various kinds of photochemistry-related applications of g-
also revealed that the existence of silica templates can prolong the C3 N4 , the decisive optical properties, including Ultraviolet–visible
lifetime of excited charge carriers by about hundreds of picosec- (UV/Vis) absorption, photoluminescence (PL) and electrochemilu-
onds, thereby achieving the high photocatalytic activities (Fig. 17b) minescence (ECL), have been readily further revealed by means
[188]. More recently, it was demonstrated that the charge separate of the theoretical calculations or experimental characterizations
efficiency in g-C3 N4 -based photocatalysts could be also revealed [47,55,187]. The typical UV/Vis absorption spectrum of g-C3 N4 pre-
by the SPV measurement, as an advanced and facile technology. As pared at different temperature were displayed in Fig. 19a [44].
shown in Fig. 18, the obviously increased SPV signal in the range Indeed, the absorption edge of conventional g-C3 N4 shows an
82 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 19. (a) UV/Vis absorption spectra of g-C3 N4 prepared at different temperature. Inset: photograph of the photocatalyst [44]; (b) the room-temperature PL spectrum
of g-C3 N4 solid powder (␭ = 365 nm, top figure) and the ECL spectrum of g-C3 N4 -modified electrode in 0.10 M K2 SO4 and 3.0 mM K2 S2 O8 solution by cycling the potential
between 0.00 and −1.30 V (vs. Ag/AgCl) with a scan rate of 100 mV/s and step potential of 1 mV (bottom figure) [78].

obvious red shift towards longer wavelengths with increasing luminophore for ECL sensing to achieve the sensitive and selective
condensation temperatures, indicating that the increasing poly- detection of trace metal ions, such as Cu2+ . Therefore, it is natu-
merization degrees can achieve a decreasing bandgap [44,196]. The rally expected that the metal-free and non-toxic g-C3 N4 could be
results are also consistent with those obtained by the theoretical extensively utilized as a multifunctional optical material for light
calculations. Furthermore, it can be seen that these two samples emitting devices [62,63], bioimaging, [100,142,204,205] ECL sens-
fabricated at 550 and 600 ◦ C exhibit very similar strong bandgap ing probe [76,78,206,207] and fluorescent probes [208–210].
absorption, with edges at approximately 450 nm. The band gap
energy (Eg ) can be further obtained according to the intercept of 3.6. Adsorption properties
the tangents to the plots of (␣h␯)1/2 vs. photon energy [146,148].
The bandgap of the condensed g-C3 N4 prepared at 550 ◦ C is esti- Generally speaking, adsorption property of a given adsorbent
mated to be 2.7 eV from its UV–vis spectrum, in good agreement is strongly dependent by both its porous microtexture and sur-
with previous studies [148]. In fact, the greyish yellow color of g- face chemical property [211–215]. Similar to the 2D graphene or
C3 N4 can further confirmed the favorable medium band gap for graphene oxide materials, a wide variety of targeted adsorbates
visible light absorption, as observed in the inset of Fig. 19a. More can be adsorpted on the multiple different functional groups (e.g.,
interestingly, other modification strategies, such as doping by Fe, amino groups) and defect sites on g-C3 N4 through different types
S, P, C, I, O and B atomics (as shown in [16]) and barbituric acid of interactions such as physical adsorption (␲-␲ stacking inter-
moleculares [84] can also lead to a redshift of the adsorption edges. action), electrostatic attraction, or chemical interaction (surface
Apart from UV/Vis absorption spectrum of g-C3 N4 , intensive complexation or acid-base interactions) [216]. Due to the weaker
investigation also focus on its PL and ECL spectrum, due to its ␲-␲ stacking interaction in the physical adsorption, the stronger
semiconductor properties. Both PL and ECL spectrum of g-C3 N4 electrostatic attraction and chemical interaction have been pro-
were also displayed in Fig. 19b [78]. As observed in Fig. 19b (top posed to the improved adsorption properties of g-C3 N4 , which will
figure), the room-temperature PL spectrum of g-C3 N4 solid pow- be thoroughly discussed in this section.
der at ␭ = 365 nm, exhibited a strong blue emission band ranging Based on the electrostatic attraction, it has been demonstrated
from 400 to 650 nm, with a maximum peak of ca. 470 nm in the that the selective photodecomposition of anionic methyl orange
blue region. It is generally believed that the intensity of room- (MO) or cationic methyl violet (MV) and methylene blue (MB) could
temperature PL signal is employed to directly and qualitatively be achieved over positively or negatively charged TiO2 -based semi-
elucidate the recombination rate of photo-generated electrons and conductors, respectively [217–219]. Similarly, the electrostatic
holes in irradiated g-C3 N4 [155,156,197,198]. Commonly, lower attraction between the negatively charged g-C3 N4 and positively
peak intensities imply the improved charge trapping and effi- charged adsorbate molecules, such as cationic MV and MB have
ciently transferring, thus further prolonging the lifetimes of charge been proposed to achieve the selective adsorption and photo-
carriers and facilitating the enhancements in photocatalytic activ- catalysis in many studies. For example, Yu and his coworkers
ity [199–201]. It should be noted that the room-temperature PL demonstrated that the negatively charged g-C3 N4 particles exhib-
spectrum of g-C3 N4 nanosheets are sensitively and markedly deter- ited extraordinaryly higher adsorption capacity towards a cationic
mined by their condensation degree (or optical band gap), thickness MB dye than anionic MO dye in aqueous suspension [146]. Fur-
and sizes [47,100,202,203]. It was also observed in the bottom of ther results showed that the adsorption kinetics of MB on three
Fig. 19b that the g-C3 N4 -modified electrode in 0.10 M K2 SO4 and different kinds of g-C3 N4 (Fig. 20a) could be well depicted by a
3.0 mM K2 S2 O8 showed the slightly broader ECL spectrum, with a pseudo-second-order kinetic equation as follows [220]:
maximum peak at ca. 470 nm (2.6 eV), which matches closely with
the room-temperature PL spectrum of g-C3 N4 solid powder. The dqt /dt = k2 (qe − qt )2 (2)
blue ECL emission from g-C3 N4 is strong enough to be observed 2
t/qt = 1/(k2 qe ) + t/qe (3)
with naked eyes as shown in the inset of bottom Fig. 19b [78].
Although there are obvious differences between the excited state of where qt (mg g−1 ) is the adsorption amount at time t, and k2
g-C3 N4 in ECL and the room-temperature PL spectrum, the similar (g mg−1 min−1 ) is the pseudo-second-order rate constant, and qe
maximum emission peak of both types of luminescence suggested (mg g−1 ) is the maximum adsorption amount. Notably, it was
that identical ECL emission is also attributed to the band gap lumi- also revealed that the adsorption kinetics of heavy metal cationic
nescence [78]. The results clearly demonstrated that the g-C3 N4 ions and perfluorooctane sulfonate over g-C3 N4 also followed the
semiconductor could be also a new kind of efficient and promising pseudo-second-order kinetic model [157,221]. Meanwhile, it can
be also found that the Langmuir model, as compared to Freundlich
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 83

Fig. 20. Adsorption kinetics (a) and adsorption isotherms (b) of methylene blue on MCN, TCN, and UCN [146].

model, could be used to better fit the adsorption isotherms of MB than those of famous “molecular basket” adsorbents (133 mg/g)
on three g-C3 N4 samples (Fig. 20b), indicating the homogeneity of [230–232], activated carbon (3.75 mmol/g) [233] and metal organic
the adsorbent surface [146]. Differences in the adsorption activity framework (3–5 mmol/g) [234–236], implying there are still ample
of three samples towards MB can be attributed to the synergistic room to enhance the CO2 adsorption capacity of g-C3 N4 semicon-
effect of surface area and zeta potential. ductor photocatalysts. In this end, the g-C3 N4 semiconductors with
Apart from the electrostatic attraction, the chemical interaction rich basic nitrogen-containing groups, high surface areas, porous
(surface complexation or acid-base interactions) between g-C3 N4 structures and suitable band gaps seem to be very promising for
and targeted adsorbates has been widely applied in manipulat- the applications in the field of photocatalytic CO2 reduction, H2
ing the adsorption properties of g-C3 N4 . Fifty years ago, Pearson evolution and the oxidation of NOx and H2 S, because porous g-C3 N4
firstly proposed the well-known hard and soft acids and bases could simultaneously serve as light-harvesting, charge-excitation,
(HSAB) principle [222,223], stating that hard and soft acids will charge-transportation, adsorption (for acid CO2 , H+ , NOx and H2 S
interact preferentially with hard and soft bases, respectively. So molecules) and catalytic centers [237].
far, this principle has been widely employed to clarify the chemi-
adsorption interactions between various kinds of adsorbents and 3.7. Electrochemical properties
adsorbates with different acidic and basic properties [224,225].
According to the HSAB principle, it is clear that the acidic molecules As shown in Fig. 2, the photocatalytic reduction and oxida-
such as CO2 , H2 S and NOx should be readily chemically bond tion reactions on the surface of semiconductors are fundamentally
to the basic nitrogen-containing groups of g-C3 N4 . Recently, Oh electrocatalytic ones driven by the photo-generated electrons and
et al. demonstrated that the g-C3 N4 functionalized porous reduced positive holes, respectively. More interestingly, g-C3 N4 semicon-
graphene oxide aerogel could achieve a large CO2 adsorption capac- ductor itself can also serve as the multifunctional electrocatalysts
ity (0.43 mmol g−1 ) and high CO2 selectivity against N2 under with higher activity than pure carbon [238,239], which play sig-
ambient conditions, and an easy regeneration of 98% adsorpted nificant roles in achieving the improved overall photocatalytic
CO2 by simple pressure swing [226]. Importantly, the DFT calcu- efficiency. Commonly, pyridinic N atoms of g-C3 N4 with strong
lations further revealed that the strong dipole interaction induced electron-accepting ability can serve as active sites for the electro-
by electron-rich nitrogen at the microporous edges of g-C3 N4 is chemical reactions, making it a potential metal-free electrocatalyst
the critical factor for achieving the high-capacity, regenerative and [55]. Unfortunately, the moderate conductivity and poor electron
selective CO2 capture. It is highly desired that the chemoselec- transfer ability of g-C3 N4 greatly limit its electrochemical perfor-
tivity of g-C3 N4 interactions for other gases could be also further mances and applications in various electrocatalysis fields, such
tailored through effectively developing the porous structure and as O2 reduction reaction (ORR) for fuel cells [240] and H2 evolu-
increasing the content of nitrogen-containing groups on the sur- tion reaction (HER) for water splitting [241]. Consequently, in the
face of g-C3 N4 [227]. For example, Jia et al. demonstrated that a past several years, extensive research efforts have been devoted
simple oxygen-atmosphere UV irradiation could create the suffi- to the exploration of hybrid g-C3 N4 -based electrocatalysts with
cient acidic sites on hierarchically ordered macro-/mesostructured higher electroconductivity and more active sites, through several
g-C3 N4 films, such as COOH and N-oxide groups through replacing strategies, such as manipulating size, thickness and structure, cou-
its surface basic nitrogen-containing groups, [228] thereby achiev- pling with various semimetal carbon materials and doping with
ing the highly selective chemi-adsorption of basic molecules. In heteroatoms [242].
the contrary, Yu and his coworkers demonstrated that the loading It has been well accepted that surface electrocatalytic ORR over
of amine groups on g-C3 N4 through monoethanolamine solution various heterogeneous semiconductors has been found to play
treatment can successfully achieved a 3.76-times enhancements key roles in determining the photocatalytic activity of pollutant
in the adsorbed CO2 amount, as compared that of pristine g-C3 N4 degradation [20,25,243] and organic synthesis [244,245]. However,
under ambient pressure and temperature (Fig. 21), owing to the so far, most of ORR co-catalysts loaded on the surface of semi-
combination effects of both physical and chemical adsorption of conductors for photodegradation and photosynthesis are mainly
CO2 [227]. Importantly, it was also observed that the enhanced constituted of noble metal elements, such as Pt [246–248], Au
adsorption and activation (favoring the formation of nonlinear [249,250] and Ag [251,252] nanoparticles/clusters. Fortunately, it
HCO3 − ) of CO2 molecules over amine-functionalized g-C3 N4 were has been recently revealed that the N-doped nanpcarbon mate-
beneficial for the improvement of CO2 photoreduction efficiency rials, such as N/S or B/N co-doped graphene [253,254], N-doped
and selective formation of CH4 [227]. More surprisingly, the CO2 graphene/porous carbon [255], Mn3 O4 /N-doped graphene [256]
adsorption capacity of g-C3 N4 microspheres with 3D hierarchical and N-doped graphene (carbon spheres, nanoyubes or nanocages)
pores and a much higher BET surface area (550 m2 /g) could reach [257–261], exhibited excellent electrocatalytic ORR activities for
2.90 and 0.97 mmol/g at 25 and 75 ◦ C, respectively [229]. How- direct methanol fuel cells (DMFC). More interestingly, it has been
ever, even so, the CO2 adsorption capacity is still obviously lower demonstrated that the electrocatalytic 4e− ORR activities of g-C3 N4
84 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 21. (a) CO2 -capture capacities of g-C3 N4 (CN) and amine-functionalized g-C3 N4 (3CN) [227]; (b) CO2 adsorption isotherms of the mesoporous g-C3 N4 microspheres at
25 and 75 ◦ C [229].

Fig. 22. (A), (a) Free energy plots of ORR on g-C3 N4 with 0e− , 2e− , and 4e− paths (corresponding to paths I, II, and III). (b–d), Schemes of ORR’s pathway on pristine g-C3 N4
with 0e− , 2e− or 4e− participation, respectively (red areas represent the active sites facilitating ORR). (B) ORR polarization curves for various electrocatalysts on rotating
electrode at 1500 rpm in O2 -saturated 0.1 M KOH solution [69]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version
of this article.)

could be significantly enhanced via the coupling with different Similar to the ORR, the thermodynamically uphill HER, as a cen-
kinds of conductive carbon support, owing to the improved electron tral reaction in the electrochemical water splitting, always requires
accumulation and transfer on the surface of g-C3 N4 . Accordingly, suitable catalysts with high electrocatalytic activity and durability
the new-generation metal-free g-C3 N4 -carbon hybrid cathode to accelerate the sluggish kinetics. In contrast to most of Pt-free
electrocatalysts in DMFC, could achieve both the superior elec- electrocatalysts, the best-known heterogeneous Pt/C composite
trochemical ORR efficiency and the high CO/methanol tolerances has proven to be the most effective HER electrocatalyst, due to
[48]. So far, various kinds of nanostructured g-C3 N4 -carbon hybrids, their high exchange current density at low overpotentials, chemical
such as g-C3 N4 @carbon [64,69], 2D g-C3 N4 nanosheet/1D carbon inertness, versatility, high conductivity, and resistance to oxidation
nanotube [65], 2D g-C3 N4 nanosheets/graphene [66,262–264], hol- [270]. However, high cost and low abundance of the noble metal
low mesoporous g-C3 N4 nanosphere/3D graphene [265], graphene Pt dramatically restricted its practical widespread applications.
supported Co-g-C3 N4 [266] and g-C3 N4 @cobalt oxide[267] have Although the cheap and earth-abundant transition metals, such as
been extensively fabricated and demonstrated to be high-efficiency Fe, Co, Ni, W, Mo and their molecular derivatives, as Pt’s alter-
ORR electrocatalysts. For example, Qiao and coworkers theoreti- natives, have been found to display outstanding electrocatalytic
cally revealed that the limited electron transfer ability of g-C3 N4 HER activity, their low stability in acidic and basic media are unfa-
leads to the low ORR catalytic activity of pure g-C3 N4 through an vorable for the long-term operation [88,124,242,271–275]. In this
unfavorable 2e− pathway (as shown in Fig. 22A) [69], whereas, regard, metal-free g-C3 N4 /conductive carbon hybrids beyond met-
the accelerated electron transfer and increased active sites in the als have also shown great promise as attractive HER electrocatalysts
nanoporous g-C3 N4 @carbon composite could achieve a nearly 100% for water splitting reactions due to their earth abundance, tunable
of selectivity for 4e− ORR pathway in alkaline aqueous solution. The molecular structures, the unique advantages to easily fabricated
further experimental results confirmed that the g-C3 N4 @ordered a variety of nanostructures and strongly tolerance acid/alkaline
mesoporous carbon (CMK-3) exhibited a considerably lower onset environments [239]. The theoretical calculations revealed that the
potential and comparatively higher ORR current density, as com- strong electronic coupling between g-C3 N4 and graphene could sig-
pared to those of g-C3 N4 (m) and the g-C3 N4 /CMK-3 mixture nificantly improve electron conductivity and optical absorption of
electrodes (as shown in Fig. 22B). By the same way, the hybrid of g-C3 N4 , thus leading to the greatly promoted charge separation
g-C3 N4 and conductive metal has also been found to significantly and transfer at the graphene/g-C3 N4 interface [276]. Subsequently,
improve its the sluggish cathodic ORR in fuel cells [241,268,269]. Qiao and co-workers further experimentally verified that the as-
At this point, it is highly desired that more and more metal- constructed multilayered g-C3 N4 nanodomains on nitrogen doped
free g-C3 N4 /carbon and earth-abundant metal/g-C3 N4 hybrid ORR ultrathin graphene sheets (C3 N4 @NG) exhibited superior HER
electrocatalysts could be exploited and utilized as co-catalysts to activity, achieving a 10-mA cm−2 HER current density at an overpo-
greatly facilitate the photocatalytic activity of pollutant degrada- tential of ∼240 mV (as shown in Fig. 23a) [239]. From the viewpoint
tion and organic transformation. of thermodynamics, compared to too strong and weak chemical
adsorption of H* on g-C3 N4 and N-graphene with the Gibbs free-
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 85

Fig. 23. (a) The HER polarization curves of g-C3 N4 , NG, g-C3 N4 /NG mixture, 33 wt% of g-C3 N4 @NG and referenced 20% Pt/C smaples (electrolyte: 0.5 M H2 SO4 , scan rate:
5 mV s−1 ). (b) The calculated Gibbs free-energy for chemical adsorption of H* on three metal-free catalysts and Pt reference at the equilibrium potential. (c) Volcano plots of i0
as a function of the GH∗ for the C3 N4 @NG (red triangle), various metals (open symbols) and a nanostructured MoS2 electrocatalyst (closed symbol) [239]. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.)

energy of −0.54 and 0.57 eV (Fig. 23b), respectively, the C3 N4 @NG and extend their applications, various fabrication methods and
hybrid with the Gibbs free-energy of about 0.19 eV, exhibits a medi- modification strategies of g-C3 N4 films have been widely devel-
ated adsorption–desorption behavior, facilitating the overall HER oped [43]. For example, Zhang et al. achievedan almost 3-fold
kinetics. In additional, as displayed in the volcano plot (Fig. 23c), the higher cathodic PEC activity for hydrogen evolution from water
HER activity of metal-free C3 N4 @NG is very close to those of famous than that of the pure g-C3 N4 through simultaneously fabricating
MoS2 electrocatalysts. It was also demonstrated that the broken a sponge-like structure and incorporating active carbon-dopant
N–3C bonds at the edge of g-C3 N4 lead to the formation of defect sites, under simulated solar-irradiation [279]. They attributed the
sites, pyridinic nitrogens, which could act as the stable H* adsorp- enhanced activity to the increased charge mobility, surface area,
tion sites and electrocatalytic HER active sites [239]. Inspired by mass transfer, active sites and ␲-conjugated structure. Further-
this interesting work, Qu and co-workers developed a more active more, the g-C3 N4 -based composite photoelectrode films such as
3D porous HER elctrocatalyst based on the hybrid of 1D g-C3 N4 g-C3 N4 /CuInS2 [280], TiO2 /g-C3 N4 [281–283], CdS/g-C3 N4 [284],
nanoribbons and 2D graphene sheets, exhibiting a current den- g-C3 N4 /WO3 [285–287], g-C3 N4 /N-doped graphene/NiFe-layered
sity of 10 mA cm−2 at an overpotential of ∼207 mV, in 0.5 M H2 SO4 double hydroxide [288], Fe2 O3 /g-C3 N4 [289], and g-C3 N4 /MoS2
solution [277]. It is believed that the high activity was attributed [290], also exhibited significantly enhanced PEC activity for hydro-
to the increased proton binding sites on 1D g-C3 N4 nanoribbons, gen evolution or water oxidation, due to the promoted charge
close contact between g-C3 N4 and graphene, and unique 3D porous separation, enhanced visible-light absorption, accelerated surface
networks for improved mass transfer and diffusion. More recently, reaction kinetics and suppressed photocorrosion. For example,
the supramolecular Cu-doped g-C3 N4 , as a biomimetic HER elec- Feng and coworkers demonstrated that the as-fabricated WO3
trocatalyst, has been also demonstrated to show a high current nanosheet Array/g-C3 N4 /CoOx layered heterojunction photoanode
density of 10 mA cm−2 at a low overpotential of 0.39 V in acidic exhibited a photocurrent density of 3.61 mA cm−2 at 1.6 V vs. NHE
media [278]. Thus, developing the novel non-noble-metal g-C3 N4 - (as shown in Fig. 24a) [285]. It is suggested that the increased
based HER electrocatalysts with high stability and activity is still a light-harvesting ability, unique 3D nanostructures with 2D layered
promising direction in the near future. nano-junctions, accelerated water oxidation kinetics, and excel-
lent charge transfer and separation are the possible reasons for the
enhanced PEC water-oxidation activity (as shown in Fig. 24b). Addi-
3.8. Photoelectrochemical properties tionally, the g-C3 N4 -based films have also been widely applied in
the PEC degradation of organic pollutants [291–296]. Typically, Zhu
Besides direct utilization as electrocatalysts, g-C3 N4 has proven and coworkers demonstrated that the g-C3 N4 film could achieve the
to be a promising photoelectrode candidate for solar energy removal of 89.3% of the total organic carbon (TOC) under a 2.5 V bias,
conversion in the PEC cells, due to its superior chemical and which was 2.4 times higher than that of photocatalytic degrada-
thermal stability and suitable electronic band structure. Initially, tion [293]. It is believed that the dramatic enhancement in activity
Zhang and Antonietti firstly observed the maximum cathodic pho- can be attributed to the promoted activity of electrocatalytic (EC)
tocurrent response (up to ca. 50 mA cm−2 at −0.3 V, IPCE ∼ 3% at oxidation, improved charge separation, and increased reactive rad-
420 nm) of bulk mpg-C3 N4 film in KCl aqueous solution contain- ical species, such as OH and O2 − , due to the combination effects of
ing Fe(II) ions, under visible light (␭ > 420 nm, 150 W Xe lamp) photocatalysis and electrocatalysis. Thus, in the near future, it is
[181]. The flat band potential (Efb ) of different g-C3 N4 semicon- naturally expected that the g-C3 N4 -based films can be widely used
ductors can also be further estimated from the onset photocurrent in more and more PEC fields, and their activity should be further
potential. More importantly, a tripled maximum photocurrent improved through better balancing electronic structures (e.g. band-
was also observed for the binary composite film of mpg-C3 N4 gap and redox ability), stability, change-carrier mobility and active
and standard Degussa P25 TiO2 (as the electron-transport chan- sites, surface area.
nel) under the same conditions. However, the unfavorable factors
of bulk g-C3 N4 film in this study, such as larger domain sizes,
grain boundary defects and textural effects, implying there is 4. Design strategies of g-C3 N4 -based photocatalysts
still ample room to further optimize the g-C3 N4 photoelectrodes.
Similarly, the weak transient photocurrent response of differ- Although the multi-function properties endow g-C3 N4 a bright
ent bulk or modified g-C3 N4 solids was extensively confirmed in future in the various kinds of photocatalytic applications, low quan-
other works [84,114,123], which is generally used to identify the tum efficiency limits its practical utilization in a large scale. To
enhanced photocatalytic activity and charge separation as an aux- date, tremendous efforts have been made to improve the photo-
iliary tool. To further improved the PEC properties of g-C3 N4 films catalytic efficiency of g-C3 N4 through different design strategies,
86 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 24. (a) Variation of photocurrent density versus applied voltage. Number lables (3), (2), and (1) data represent the hybrid 3D WO3 /C3 N4 //CoOx , WO3 /C3 N4 , and WO3 ,
respectively. (b) Energy diagram and expected charge flow of WO3 /C3 N4 [285].

transport and separation rate [106]. Recently, Zhu and cowork-

ers demonstrated that the K+ doping could decrease the VB level
of g-C3 N4 , thus resulting in enhanced separation and immigra-
tion of photo-generated carriers under visible light [305]. More
recently, Dong and coworkers revealed that K atoms could achieve
an interlayer doping (as shown in Fig. 26b), instead of the cave
doping of Na atoms in g-C3 N4 [306]. It is believed that K atoms can
bridge the two adjacent g-C3 N4 layers, which lead to the narrowed
band gap, extended ␲ conjugated systems, and positive-shifted
valence band position, thus achieving the increased visible-light
harvesting, efficient charge separation, and strong oxidation capa-
Fig. 25. Summary of band-gap engineering for g-C3 N4 .
bility, respectively. In contrary, despite of the increased in-planar
electron density and visible-light absorption, the cave doping of
including band-gap engineering, defect control, pore texture tai-
Na atoms still exhibits high recombination rate of carriers in the
loring, dimensionality tuning, surface sensitization, heterojunction
g-C3 N4 planes, thus resulting in the reduced photocatalytic perfor-
construction, co-catalyst and nanocarbon loading, which will be
mance [306]. This work might provide new insights into the deep
systematically discussed in this section.
understanding on the metal doping of g-C3 N4 and the design of
electronically optimized layered photocatalysts for enhanced solar
4.1. Band-gap engineering
energy conversion.
Apart from metal doping, the non-metal doping of g-C3 N4 has
In general, it is known that the ideal bandgap of a semicon-
been majorly realized through the chemically substituted doping.
ductor should be ∼2.0 eV, which could harvest a variety of visible
As displayed in Fig. 16, almost all the non-metal doping, such as
light to generate sufficient electrons and holes with strong driv-
S [118,182,307–311], P [183,312–316], B [114,317–320], O [184],
ing forces for photocatalytic redox reactions [7,10]. However, the
C [185], and I [128,186], could narrow the bandgap of g-C3 N4 and
2.7 eV bandgap of g-C3 N4 make it only utilize the solar light with
enhance its light harvesting capability. In general, the C self-doping
wavelength below 460 nm. Thus, in order to further enhance the
can substitute the bridging N atoms [185], whereas the O [184,321],
light harvesting ability of g-C3 N4 , various band-gap engineering
S [307,309,322] and I [128,186] doping could achieve the replace-
strategies, including atom-level (foreign metal and non-metal ele-
ment of N atoms in the aromatic triazine rings (as shown in Fig. 27).
ments) and molecular-level (copolymerization) doping, have been
Interestingly, the doping of these different elements can promote
widely exploited and demonstrated to achieve the enhanced photo-
the delocalization of the ␲-conjugated electrons, which is funda-
catalytic performance [27,54], which will be summarized in Fig. 25
mentally important for improving the conductivity, mobility and
and discussed in this section.
separation of photo-generated electrons, thus greatly enhancing
As shown in Fig. 25, two possible kinds of cation doping, namely,
the photocatalytic performances of doped g-C3 N4 . In the con-
cave doping and interlayer doping have been observed. Their
trary, the substituted doping of P [183,315,316,323–326] and B
detailed doping mechanism was shown in Fig. 26. On the one
[327,328] atoms preferentially occur on the C atoms, thus lead-
hand, the metal ions (Mn+ ) can be incorporated into the large caves
ing to the formation of strong Lewis acid sites (P+ ) on the basic
(the triangular pores) between the connected triazine structures
surface (from amine or imine groups) of g-C3 N4 , due to the intrin-
in the plane of g-C3 N4 (as shown in Fig. 26a), through the strong
sic polarization of P–N bond and delocalization of one extra lone
coordination interactions between them and negatively charged
electron in electron-rich P atom [324]. Most recently, Qiao’s group
nitrogen atoms, thus achieving the so-called cave doping [297].
demonstrated that the P-doping of porous g-C3 N4 nanosheets can
The previous studies revealed that the transition metal ions, such
drastically narrow the intrinsic band gap from 2.98 to 2.66 eV and
as Fe3+ , Zn2+ , Mn3+ , Co3+ , Ni3+ and Cu2+ can be doped into the
promote the photo-excitation of electrons from the VB of P-doped
large caves of g-C3 N4 [245,298–303]. The DFT calculations demon-
g-C3 N4 , due to the formation of vacant midgap states below the
strated that the cave doping of Pt and Pd atoms could effectively
CB minimum of g-C3 N4 through the hybridization of C 2s2p, N
improve the carrier mobility, narrow the bandgap or optical gap,
2s2p and P 3s3p, thus enhancing visible light absorption [326].
and enhance the light absorption, which are favorable for photocat-
Meanwhile, it was also demonstrated that the (NH4 )2 HPO4 as phos-
alytic reactions [304]. More interestingly, it was revealed that the
phorus precursor could achieve the cave doping (in the interstitial
cave doping of alkali-metal ions such as Li+ , Na+ , and K+ will induce
sites, as shown in Fig. 27). Furthermore, it is well known that S
the un-uniform spatial charge distribution in different intercalated
atoms have been found to preferentially substitute N atoms with a
regions, increase the free carrier concentration, improve charge
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 87

Fig. 26. Two kinds of metal ion doping of g-C3 N4 framework: (a) cave doping, the incorporation of metal ions (Mn + ) through the coordination interactions, Color scheme:
C, red; N, yellow [27]; (b) interlayer doping (the interlayer bridging pattern for K) [306]. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

Fig. 27. Possible substituted sites of non-metal doping in the single layer of g-C3 N4 .

larger electronegativity (3.04), thus leading to the decreased VB/CB comonomer) [84]. More interestingly, 2D g-C3 N4 nanosheets fab-
levels and band gap [118,182,199,307,310,329]. Nevertheless, as ricated by the one-pot condensation of urea and electron-rich
special cases, in situ sulfur and boron doping of g-C3 N4 has also thiophene co-monomers could achieve the highest quantum effi-
been found to replace the C and N atoms in the rings, respec- ciency of 8.8% at 420 nm for H2 generation, (Fig. 28b) owing to
tively [182,330]. In addition, the F doping (NH4 F as a cheap fluorine the narrowed band gap, improved electron migration and through
source) can achieve the formation of the C F bonding in g-C3 N4 the formation of surface dyadic structures [129,342]. In contrary,
(as shown in Fig. 27), thus lowering the electronic band gaps [331]. the molecular doping by an electron-deficient pyromellitic dianhy-
However, it should be point out that excessive doping of nonmetal dride could thereby enhance the strong photooxidation capability
and metal is found to be detrimental to enhance the photocatalysis, of g-C3 N4 , due to greatly decreased both the CB and VB posi-
because the more defects can also act as the recombination centers tions [343]. To sum up, as a unique bottom-up way for tailoring
of electron–hole pairs. In future, the co-doping of different metals the bandgap of g-C3 N4 , the copolymerization approach provides
and/or nonmetals, such as Fe/P [332] S/Co/O [333], S/P [334], P/O more opportunities for designing highly effective polymeric pho-
[335], K/Na [336] and C/Fe [337] deserves more attention, due to tocatalysts with desired electrical properties and band gap through
their positive synergetic effects on the visible-light absorption and incorporating structure-matching organic moleculars, which also
photocatalytic properties. provides insights into the mechanism of heterogeneous photocatal-
In addition, copolymerization at molecular level was also widely ysis of organic semiconductors at molecular levels.
employed to strongly enhance the photocatalytic activity of g-C3 N4 ,
via simultaneously modulating its band gap, electronic structures 4.2. Defect control
and physical and chemical properties. Commonly, it is believed
that the copolymerization modification with structure-matching It is widely accepted that a high degree of crystallinity is
aromatic compounds or organic additives could increase the advantageous for enhancing the photocatalytic redox reactions,
desired delocalization of ␲-conjugated electrons and improve the as compared to the negative roles of defects as charge-
intrinsic drawbacks in g-C3 N4 , thus maximizing the photochem- recombination sites [7]. For example, ionothermal synthesis
ical activities [54,338–341]. For example, Wang and co-workers [102,103,105,108,344,345] thermal polymerization in ammonia
demonstrated that the tunable bandgaps of tri-striazine-based [346] and microwave-assisted heating synthesis [112,113] have
g-C3 N4 ranging from 2.67 to 1.58 eV could be obtained (as been broadly employed to achieve the highly crystalline g-C3 N4 for
shown in Fig. 28a) through the copolymerization of dicyandi- efficient photocatalytic hydrogen evolution. It is believed that the
amide (monomer) and different amounts of barbituric acid (BA, enhanced crystallinity of g-C3 N4 could improve the charge-carrier
88 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 28. (a) UV–vis absoprtion spectra of g-C3 N4 and CNBx (arrow direction, x = 0.05, 0.1, 0.2, 0.5, 1, 2), where x refers to the weight ration of barbituric acid [84]. (b) H2
evolution over different g-C3 N4 copolymerized by urea and various monomers (3wt%Pt as co-catalyst) [129].

Fig. 29. (a) UV–vis absorption spectra g-C3 N4 (GCN) and amorphous g-C3 N4 (ACN). Inset: Schematic of monolayer crystalline GCN and ACN; (b) The detailed band structures
of GCN and CAN, as well as the redox potentials of water splitting [348].

Fig. 30. (a) Lateral view and (b) vertical view for the interactions between water and a layer of defect g-C3 N4 sheet. Red, white, gray and white spheres represent O, H, C
and N atoms, respectively. (c) Spatial distribution functions of O and H atoms projected onto the defect g-C3 N4 sheet within the first layer [353]. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

mobility and separation, thus leading to significantly improved amorphous g-C3 N4 could effectively narrow its bandgap from 2.7
photoactivity. However, more recently, as an effective strategy, to 1.9 eV, corresponding to an obvious red-shift of absorption edge
the creation of nitrogen vacancies [347] or amorphous structures from 460 to 682 nm (as shown in Fig. 29a). The further valence
[348] in g-C3 N4 , has been extensively demonstrated to improve the band XPS analysis reveals that the levels of VB and CB could be
visible-light activity, owing to the efficiently extended absorption reduced by 0.31 and 0.61 eV, respectively, without affecting the
edge and promoted lifetime of charge carriers. For example, Liu and thermodynamic requirements for O2 evolution and water reduc-
co-workers demonstrated the high-temperature Ar-atmosphere tion (as shown in Fig. 29b). These results could open up new ways
treatment of bulk g-C3 N4 at 620 ◦ C could disrupt the weak inter- to develop visible light-driven amorphous or defective g-C3 N4 pho-
actions of hydrogen bonds and van der Waals forces, and destroy tocatalysts.
the long-range order in crystalline g-C3 N4 structures, thus fabricat- Apart from Ar-atmosphere heat treatment, the high-
ing the amorphous g-C3 N4 with the short-range order (as shown temperature treatment of pristine g-C3 N4 in a H2 , NH3 or
in the inset of Fig. 29a) [348]. Such structure disorder changes in vacuum atmosphere could also create nitrogen or carbon vacan-
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 89

cies in carbon nitrides, thus achieving the narrowed band gap 1 [369]) have been available in developing highly porous g-C3 N4 .
and improved photocatalytic performances [347,349–351]. For Absolutely, the mesoporous silica materials have been demon-
example, a novel g-C3 N4 photocatalyst with N-vacancy struc- strated to be the most widely used hard templates. Unfortunately,
tures and a bandgap of 2.03 eV could be fabricated by heating the trapped air and the weak-acid walls of mesopores in the silica
the melon in a H2 atmosphere [347], which exhibits promising templates greatly prevent the infiltration and fast mass diffusion
photocatalytic activities towards generating • OH radicals and of basic organic precursor molecules into them, thus leading to the
decomposing the organic pollutant Rhodamine B. It is believed incomplete utilization of their porous structures and the limited
that the nitrogen-vacancy defects could greatly widen visible light enhancement in the surface area of porous g-C3 N4 [59]. Thus, to
absorption range and suppress the unexpected fast recombination maximize the roles of porous silica templates, Zhang et al. demon-
of photo-excited carriers, thus achieving the improved photoac- strated that the combined strategy of dilute HCl pretreatment of
tivity. Similarly, it was also demonstrated that the introduction of SBA-15 and sonication-vacuum insertion could increase the surface
hydrogenated defects in g-C3 N4 nanosheets could greatly enhance area of mesoporous g-C3 N4 up to 517 m2 g−1 , due to the improved
the photocatalytic hydrogen evolution [349,352]. Furthermore, a surface reactivity of the silica and removed trapped air [360]. How-
simple thermal treatment under an NH3 atmosphere can not only ever, the hazardous agents for removing the silica templates, such
develop highly porous g-C3 N4 nanosheets with plenary carbon as NH4 F or HF, are harmful for environment, g-C3 N4 itself or other
vacancies through etching their lattice carbon sites by the reactive materials in a g-C3 N4 -based composite photocatalysts, restricting
radicals from the NH3 decomposition [350,351], but also can the practical applications of hard-templating strategy in a large
enhance the surface area, porosity and crystallinity of condensed scale. Thus, it is expected that more and more easy-removal or non-
g-C3 N4 , due to the greatly reduced N defects in the ␲-conjugated removable hard templates, such as CaCO3 , Al2 O3 , Fe2 O3 and various
network [346]. More interestingly, through employing both DFT nanocarbons, should be further developed and applied in the fab-
and molecular dynamics calculations, Wu et al. indicated that ricating the highly porous g-C3 N4 with different nanostructures
the defect within g-C3 N4 played a key role in the adsorption [69].
and dissociation of water, whereas, water does not dissociate on The “greener” soft-template route is also an interesting strat-
the perfect g-C3 N4 sheet (as shown in Fig. 30) [353]. However, egy to avoid various kinds of unfavorable factors aforementioned
it should be noted that the excessive nitrogen vacancies as the for the hard-templating methods, which has also witnessed great
recombination centers could be also harmful for the photocatalysis advances in developing porous g-C3 N4 micro-and nanostructures.
[354]. To demonstrate this point, Osterloh and co-workers found In general, the amphiphilic organic molecules are easy to form self-
that surface structure defects in g-C3 N4 , with energy levels at assembly micelles with different structures in solution, which can
+0.97 V and −0.38 V ([Link]), limit visible light driven hydrogen function as soft templates (structure directing agents) to induce the
evolution and photovoltage [191]. More interestingly, it was also growth of precursors around them and further form expected com-
demonstrated that the vacuum heat-treatment at 500 ◦ C could posite structures [54,357]. Clearly, so far, various soft templates,
obtain the highest photoactivity for H2 evolution due to the such as ionic liquids [114,373], Pluronic P123, [374,375] Tri-
increased content of the tri-s-triazine phase and suitable N defects ton X-100 [374,376,377], bubble [378–381,383] and biomolecules
in the tri-s-triazine ring building blocks [355], which are similar [279,382,384] have been widely utilized in the fabrication of porous
to the previous report about the vacuum-treated titanium dioxide g-C3 N4 photocatalysts. For example, Zhang et al. demonstrated
[356]. Consequently, the controlled defect concentration in g-C3 N4 that the mixture of 1-butyl-3-methylimidazolium tetrafluorob-
is crucial for achieving the ideal photoactivity. orate (BmimBF4 , as a soft template) and dicyandiamide could
achieve the B/F-co-doped mesoporous g-C3 N4 with a surface area of
4.3. Pore texture tailoring 444 m2 g−1 and a large total pore volume (0.32 m2 g−1 ) [114]. Sim-
ilarly, the nanoporous g-C3 N4 fabricated by using Pluronic P123
Another attractive design strategy is to tailor the porous struc- block polymers as a soft template, could exhibit a high surface area
tures/texture of g-C3 N4 materials, which can significantly increase of 299 m2 g−1 [374]. However, the obvious disadvantages of ionic
their exposed surface area and accessible channels(porosity) and liquids and polymers, such as the high cost, unexpected carbon
active sites in g-C3 N4 , thus facilitating the molecular mass trans- residue and insolubility in water, greatly limit their extensive prac-
fer/transport, charge migration and separation, surface reactions tical applications in a large scale. At this regard, the use of bubbles
and light harvesting [83]. All these advantageous features can of water vapor as soft templates seems more promising in synthe-
benefit the enhancement of photocatalytic efficiency. So far, a sis of porous g-C3 N4 , due to the absence of impurities and post
variety of highly porous g-C3 N4 with diverse nanoarchitectures treatments [380,383]. Also, the interesting biomolecules as soft
and morphology have been widely fabricated through several templates are highly desirable in the future studies [279,382,384].
typical pathways, such as hard templating (nanocasting), soft In addition, much attention has also been paid to the
templating (self-assembly along the structure directing agents), supramolecular self-assembly and template-free methods. For the
self-templating (supramolecular self-assembly) and template-free supramolecular self-assembly strategies, it has been demonstrated
methods [27,48,54,357], which have been thoroughly summarized that the formation of hydrogen-bonded supramolecular assem-
in Table 4. The detailed comparison and discussion between them blies (or complex) between melamine precursores and triazine
will be highlighted in this section. derivatives plays key roles in determining the different nanostruc-
As observed in Table 4, it is clear that the hard templating tured morphologies of porous g-C3 N4 materials [385–388]. For the
(nanocasting) strategy is deemed to be one of the most simple and template-free route, the (hydro) solvothermal [328,394,397,398]
effective methods to construct mesoporous g-C3 N4 photocatalysts and freezing assistant assembly [395,396] methods have been
with superior high surface area (up to 517–623 m2 /g) [69,229,360]. successfully exploited to fabricat porous g-C3 N4 materials. How-
In theory, various kinds of macro/mesoporous materials with super ever, compared to the hard-templating methods, the surface area
high surface area can be employed as hard templates to con- of porous g-C3 N4 prepared by these two strategies is still much
struct porous g-C3 N4 . To date, various kinds of hard templates smaller. More importantly, there are only limited precursors which
such as porous anodic Al2 O3 [358,359], CaCO3 [370], graphene could form ordered and stable supramolecular aggregates in a sol-
oxide nanosheets, [151] CMK-3 mesoporous carbon [69], meso- vent, based on noncovalent interactions (e.g. hydrogen bonding).
porous silica (nanospheres, [123,361,363] foams, [229] SBA-15, Accordingly, it is expected that these two appealing approaches
[122,170,362] chiral silica, [365,366] silica KIT-6, [368] and KCC- could be finely controlled and combined with other strategies, such
90 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Table 4
Summarization of different fabrication methods for mesoporous g-C3 N4 .

Morphology Templates Precursor Band gap BJH pore Pore BET surface Ref. (year)
[eV] size (nm) volume area
(cm3 g−1 ) [m2 g−1 ]

Hard templating methods

Nanotubes Porous anodic Al2 O3 (AAO) EDA, CTC [358] (2009)
Nanorods membranes CA 2.9 25 [359] (2011)
Ordered mesoporous Ordered Mesoporous SBA-15 CA 2.74 5.3 0.34 239 [122] (2009)
Mesoporous 12-nm SiO2 particles CA 2.7 373 [123] (2009)
8.3 0.41 126
Ordered mesoporous SBA-15 pre-treated with 1 M HCl CA 3.4 0.49 517 [360] (2013)
Hierarchical mesostructures Mesostructured cellular silica foams EDA, CTC 4/43 0.9 550 [229] (2010)
Inverse opal Uniform-sized silica CA 20 0.79 230 [361]
structures nanospheres 70 1.7 140 (2011)
Mesoporous SBA-15 nanorods CA 3.9 110–200 [362] (2012)
nanorods
Ordered mesoporous SBA-15 ATC 2.78 5.3 0.34 239 [170] (2011)
Mesoporous 12-nm SiO2 particles ATC 0.77 176 [363] (2012)
Hollow nanospheres Monodisperse silica@ mesoporous CA 2.9 79 [364] (2012)
silica
Helical rodlike Chiral mesoporous silica CA 2.75 3.8/10.7 56 [365] (2014)
Porous nanorod Chiral silica CA 2.7 52 [366] (2014)
nanorods
Mesoporous 7 nm colloidal silica particles Urea 7 224 [367] (2012)
sphere
Porous composite Graphene oxide sheets MA 2.7 17.6 0.09 26.6 [151] (2011)
g-C3 N4 @CMK-3 composite CMK-3 mesoporous carbon CA 3.0 0.49 623 [69] (2011)
Cubic mesoporous Ordered mesoporous silica KIT-6 CA 3.6 0.4 208 [368] (2010)
Nanosheet-based nanospheres KCC-1 silica spheres CA 2.86 3.8 0.4 160 [369] (2014)
Porous CaCO3 DCDA 38.6 [370] (2015)
Porous ZnCl2 DCDA 2.89 0.08 46 [371] (2015)
Macroscopic 3D Porous monolith MA sponge Urea 0.76 78 [372] (2015)

Soft templating methods

Sponge-like mesopore Ionic liquids(BmimBF4 ) DCDA 0.32 444 [114] (2010)
Porous nanosheets BmimBF4 Urea 25.0 23.4 0.40 0.51 73 90 [373] (2014)
BMIM-PF6 DCDA [312] (2010)
Nanoporous BmimDCN DCDA 5.6 0.179 81 [374] (2010)
Worm-like Pluronic P123 MA 1.55 90 [375] (2012)
porous
Nanoporous Pluronic P123 DCDA 0.128 299 [374] (2010)
Nanoporous Triton X-100 DCDA 3.8 0.284 116 [374] (2010)
Bimodal mesoporous Triton X-100 MA, GA 3.8/10–40 [376] (2011)
Nanoporous Triton X-100 MA sulfate 2.47–2.57 50–135 [377] (2014)
Bubble (urea) DCDA 60 [378] (2014)
Nanoporous Bubble (thiourea) DCDA 2.72 3.7 46.4 [379] (2013)
Porous Bubble (water vapor) Urea 18.2 0.321 69.6 [380] (2012)
Sponge-like Ammonium alginate or gelatin DCDA 2.49 63 [279] (2013)
Mesopore Bubble (sublimed sulfur) MA 50 46 [381] (2015)
Mesopore Bubble (sucrose) MA 13.2 0.355 121 [382] (2015)
Honeycomb-like Bubble (water) urea 2.65 0.68 106 [383] (2015)
Diatom-structure Diatomite CA 5 [384] (2013)

Self-templating (Supramolecular self-assembly) methods

Hollow box Self-assembly CAA/MA 45 [110] (2013)
Hollow spheres Self-assembly MA/CAA 30–40 0.4 77 [107] (2013)
Spherical particles Self-assembly MA/CAA 2.79 0.3 66 [385] (2013)
Hollow tube-like Self-assembly CAA/MA 41 [386] (2015)
Hollow to wormlike Self-assembly MA, urea, CAA 2.73 12.84 0.31 97.4 [387] (2014)
Fiber-type/sheet-like Self-assembly CA, MA, DPT 2.25 75 ± 5 [111] (2014)
Roll-like Self-assembly CAA, MA, BA 60–70 [388] (2014)
Crystalline Self-assembly MA, TAP 119 [108] (2014)
Porous Self-assembly CAA/MA 2.7 77 [389] (2014)

Template-free methods
Nanobelts MA [390] (2011)
Porous MA hydrochloride 2.83 69 [391] (2012)
Porous DCDA 2.72 15.8 0.50 201 [392] (2013)
Hierarchical structure MA 2.74 35.6 [393] (2014)
Nanoporous Ball milling/hydrothermal method MA 2.75 0.15 30.9 [394] (2015)
Nanosheets urea 2.78 1.41 288 [153] (2013)
Seaweed-like architecture Freezing assistant assembly DCDA <20 130 [395] (2015)
Monolayer mesoporous Freezing assistant assembly/exfoliation DCDA 2.75 <20 331 [396] (2016)
Porous microspheres Solvothermal in acetonitrile (200 ◦ C) CAC/MA 2.42 8.5 [397] (2015)
Nanosheets Urea, Ph4 BNa 2.83 16.2 0.62 144 [328] (2013)
Nanorod-network superstructures Solvothermal in acetonitrile (180 ◦ C) CAC/MA 1.92 30 [398] (2012)

BmimBF4 : 1-butyl-3methylimidazolium tetrafluoroborate; BMIM-PF6: 1-butyl3-methylimidazolium hexafluorophosphate; BmimDCN Ph4 BNa: sodium tetraphenylboron;
CA: cyanamide; MA: melamine; DCDA: Dicyandiamide; CAA: cyanuric acid; CAC: Cyanuric chloride; DPT: 2,4-diamino-6-phenyl-1,3,5-triazine; BA: barbituric acid; ATC:
ammonium thiocyanate; EDA: ethylenediamine; CTC: carbon tetrachloride; GA: glutaraldehyde, TAP: 2,4,6-triaminopyrimidine.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 91

as an infrared heating process [399] or a simple reflux method mixing, thus leading to the enhanced exfoliation efficiency of bulk
[400], to design and fabricate highly efficient porous g-C3 N4 -based g-C3 N4 into 2D nanosheets [426,465]. Thus, the ultrasonication
semiconductors with high surface area and unique nanostruc- treatments in various solvents with proper surface energy, such
tures in a low-temperature solution in future research [54]. In as water (102 mJ m−2 ), methanol, ethanol, N-methyl-pyrrolidone
addition, it is also expected that the two strategies of in situ (NMP), 1-isopropanol(IPA), dimethyl formamide(DMF), acetone,
template-sacrificial dissolution [401] and chemically induced self- acetonitrile, 1,4-dioxane and their mixtures, have been applied in
transformation [217,402–408] could be applied in developing overcoming the weak van der Waals forces between the two adja-
highly porous g-C3 N4 -based semiconductors. cent g-C3 N4 layers and successfully exfoliating the bulk layered
g-C3 N4 into 2D ultrathin nanosheets [100,103,178,416,425,426].
4.4. Dimensionality tuning For example, Xie and coworkers successfully prepared the ultrathin
g-C3 N4 nanosheets (0.15 mg/mL) with a size distribution rang-
Generally, compared with the bulk counterparts, nanos- ing from 70 to 160 nm and a height of ∼2.5 nm (about 7 layers)
tructured g-C3 N4 semiconductors with unique dimensions and by a “green” liquid exfoliation route from bulk g-C3 N4 in water
configurations could exhibit several obvious advantages for solar for the first time (as shown in Fig. 31a and b) [100]. To further
photocatalysis, such as the higher surface area, shorter charge enhance the dispersion concentration of exfoliated mono-layer or
migration length, higher solubility and tunable electronic struc- few-layer g-C3 N4 nanosheets, the better solvent effects of organic
ture [37]. Detailedly speaking, the charge carriers generated in and mixed solvents have been utilized to exfoliate the bulk C3 N4
the ultrathin g-C3 N4 nanosheets can readily reach their surface materials [424,429]. For example, the exfoliation of commercial
for redox reactions through the very short paths, as compared g-C3 N4 in the mixed solution (ethanolamine, 1,3-butanediol and
to traditional 3D bulk g-C3 N4 semiconductors, thus achieving 3-pyridinemethanol) could obtain the 7-layer g-C3 N4 nanosheets
the rapid charge separation. More importantly, through control- with a concentration of 1 mg/mL [429]. In another example, the
ling the layer number without changing the atomic structure, single layer of g-C3 N4 nanosheets with a concentration of 3 mg/mL
the energy band structure of g-C3 N4 could be effectively tai- have been achieved through the effective exfoliation in the mixed
lored due to the quantum confinement effects, thus leading to water/organic solvents [424]. However, some typical problems,
improved activity and selectivity for various reactions, such as CO2 including the use of organic solvents and additives, long ultra-
reduction [409] and O2 reduction [410]. In addition, the nanostruc- sonication exfoliation time and low yield, still need to be further
tured g-C3 N4 with different dimensions also exhibited significantly overcome. Thus, the liquid ammonia-assisted lithiation and the
enhanced opened-up surface areas and highly exposed active intercalation of LiCl ions have been exploited to achieve the large-
sites, thereby greatly facilitating the photocatalytic enhancements. scale exfoliation of bulk g-C3 N4 materials [430,431]. Especailly, the
All these advanced features endow the nanostructured g-C3 N4 8-layer-thick O-doped g-C3 N4 nanosheets could be fabricated by
with attractive structure-dependent, morphology-dependent and this liquid ammonia-assisted lithiation method in a large scale
thickness-dependent applications ranging from photocatalysis to (10 g) and high yield (85%), under mild conditions [430]. More
other emerging fields. Thus, as a simple way, tuning physical fortunately, it was demonstrated that the chemical exfoliation in
dimensions of g-C3 N4 has become a popular strategy to manipu- acid or alkaline solution could not only obtain amphoteric single-
late the optical, electrical, and redox properties, thus achieving the layer g-C3 N4 nanosheets with the negatively charged carboxyl and
desired catalytic activity, selectivity, and long-term stability. So far, positively charged −NH2 /NH3 + groups, but also efficiently reduce
nanostructured g-C3 N4 with various different dimensionality, such the ultrasonication-treatment time from more than 10 h to 2 h
as 0D quantum dots [411–414], 1D nanowires/nanorods/nanotubes [82,178,432,470]. For example, Xu et al. successfully obtained sin-
[138,277,359,395,400], 2D nanosheets [100,415,416], 3D hierar- gle layer of g-C3 N4 nanosheets with a thickness of 0.4 nm by
chical structures [393,417–419] have been widely exploited and means of the rapid exothermic effect of the intercalated concen-
applied in the photocatalysis [55]. Among them, the 2D ultrathin trated H2 SO4 (98%) dissolving in deionized water [178]. Following
g-C3 N4 nanosheets have proven to be more promising for various this report, Tong et al. developed an interesting high-throughput
photocatalytic applications [27,52,56], whose fabrication strategies method to rapidly fabricate g-C3 N4 nanosheets through combin-
will be highlighted in this section. ing the oxidation, protonation and heating effects of concentrated
Generally, the free-standing ultrathin g-C3 N4 nanosheets could H2 SO4 [432]. The g-C3 N4 nanosheets with a thickness of 2.5 nm
be obtained via two distinct synthetic strategies, including the and different degree of exfoliation could be easily achieved though
top-down exfoliation of layered bulk g-C3 N4 materials and bottom- directly adding controlled amount of H2 O into a bulk g-C3 N4
up assembly of precursors (molecular building blocks) in a 2D suspension using the concentrated H2 SO4 as solvent. This facile
manner [52,56]. Typically, these two fabrication strategies can acid-exfoliation method with low cost and controlled exfoliation
be further classified into five detailed categories: ultrasonication- degree would open up new opportunities for the large-scale fabri-
assisted liquid exfoliation, chemical exfoliation, thermal oxidation cation and extensive application of g-C3 N4 nanosheets.
etching, combined and other approaches. In order to facilitate Although bulk g-C3 N4 could be also easily thermally exfoliated
further comparison, various different fabrication methods for g- into 2 nm-thickness nanosheets (around 6–7 layers) through the
C3 N4 nanosheets have been thoroughly summarized in Table 5. As direct oxidation “etching” [415], the poor yield (<6%) and significant
observed in Table 5, it is clear that the 2D single-layer and few-layer interface defects, thus leading to the significantly reduced pho-
g-C3 N4 nanosheets could exhibit much higher surface areas in the toability and photoactivity. Motivated by the successful thermal
range from 50 to 384 m2 g−1 , which are several times larger than exfoliation of the NH4 Cl-intercalation g-C3 N4 materials [449], Wu
that of bulk layered g-C3 N4 (10 m2 g−1 ), thus significantly favoring and coworkers recently developed a facile one-step dicyandiamide-
the photocatalytic enhancement. blowing method with NH4 Cl as the gas template to achieve the
Inspired by the formation of graphene/metal dichalco- scalable fabrication of high quality 2D g-C3 N4 nanosheets [443].
genide/double hydroxide nanosheets by liquid exfoliation of As shown in Fig. 32, it is believed that the gases (NH3 and
layered bulk counterparts [463–469], it is highly expected that the HCl) released from NH4 Cl during heating directly achieved the
mono- or few-layer C3 N4 nanosheets could be obtained through fast exfoliation of bulk g-C3 N4 into the crinkly 8-layer g-C3 N4
a simple liquid exfoliation of bulk layered g-C3 N4 by sonication. nanosheets (with a thickness of 3.1 nm and a high band gap of
Clearly, the well matched surface energy between a liquid solvent 2.83 eV). Other methods such as thermal exfoliation of C3 N4 -based
and g-C3 N4 (115 mJ m−2 ) could effectively reduce their enthalpy of intercalation compound [449], microwave heating [462] and ball
92 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Table 5
Summarization of different fabrication methods for g-C3 N4 nanosheets.

Bulk g-C3 N4 Solvents, bulk powder/solvent Concentration Thickess (nm) /Layer Band gap (eV) /surface Ref. (year)
(mg/ml), time (h) (mg/mL)/Yield (%) numbers area (m2 g−1 )

Ultrasonication-assisted liquid exfoliation

MA (P, 600 ◦ C) Water, 100/100, 16 h 0.15/ 2.5/7 2.70/ [100] (2013)
Poly(triazine imide) (I) Water, 2/1, 15 h 0.2/ 1–2/3–6 [103] (2014)
CA (P, 530 ◦ C) Water, 200/200, 24 h ∼1.8/5–6 2.6/ [410] (2013)
MA (P, 600 ◦ C) Water, 50/50, 10 h /14.5 1.2/4 [299,420](2013)
MA (P, 600 ◦ C) Water, 50/50, 10 h /14.5 1.0/3 [421] (2013)
◦
MA (P, 600 C) Water, 100/200, 16 h /8.6 [422] (2013)
◦
MA (P, 550 C) Water, 50/50, 2 h 1.2/<5 [423] (2014)
MA (P, 550 ◦ C) Water/organic solvents, 500/150, 10 h 3/ 0.38/1 2.79/59.4 [424] (2015)
Commercial g-C3 N4 Isopropanol, 30/10, 10 h 2/ < 9 2.65/384 [416] (2013)
(Carbodeon Ltd)
CA (P, 550 ◦ C) Ethanol, 50/50, 2 h 2–3/5–8 2.73/112.5 [425] (2014)
DCDA (P, 600 ◦ C) 1,3-butanediol, 60/25, 24 h 0.35/ 0.9–2.1/3–6 2.79/32.54 [426] (2014)
◦
MA (P, 550 C) 30 wt% isopropanol + water, 4/1, 10 h 2/6 2.70/ [427] (2014)
◦
MA (P, 600 C) Water, 100/200, 16 h /8.6 [422] (2013)
DCDA (P, 520 ◦ C) DMF, 50/200, 2h(80 ◦ C)+ melamine 2–3/6–9 2.75/116.76 [428] (2015)
Commercial g-C3 N4 Ethanolamine/1,3-butanediol/3- 1/ 7 [429] (2015)
(Carbodeon Ltd) pyridinemethanol,30/10,4h

Chemical exfoliation
MA (P, 550 ◦ C) Liquid ammonia-assisted lithiation /85% 2.5/8 2.78/22.5 [430] (2014)
MA + LiCl(P, 380 + 550 ◦ C) The intercalation of LiCl ions and the liquid 2–3/6–9 2.82/186 [431] (2016)
exfoliation in water
DCDA (P, 550 ◦ C) H2 SO4 (98 wt%) treatment for 8 h, then rapid /30% 0.4/1 2.92/205.8 [178] (2013)
exfoliation
MA (P, 550 ◦ C) H2 SO4 (98 wt%), 1000/15, 15 min /70% 2.5 2.93/86.29 [432] (2015)
DCDA (P, 550 ◦ C) H2 SO4 (98 wt%) 300/ /1 3.28/ [180] (2015)
DCDA (P, 550 ◦ C) HCl treatment for 1 h, then exfoliation for 2 h /25–30% 2–4/6–10 2.75/305 [82] (2014)
MA (P, 550 ◦ C) 6 M HCl, 320/80, hydrothermal at 110 ◦ C for 5 h /109.3 [433] (2014)
MA (P, 550 ◦ C) 0.1 M NaOH, 1000/90, hydrothermal at 150 ◦ C for /65 [164] (2013)
18 h
MA (P, 520 ◦ C) HCl treatment for 1 h, then exfoliation for 2 h /25–30% 9.0/30 3.42/ [82] (2014)
MA (P, 600 ◦ C) HNO3 (63 wt%) treatment for 2.7/179.5 [434] (2015)
8 h, then sonicated exfoliation

Thermal oxidation etching

DCDA (P, 550 ◦ C) Air, 500 ◦ C, 2 h /<6% 1.62–2.62/4–7 2.97/306 [415] (2012)
DCDA(P, 550 ◦ C) Air, 500 ◦ C, 2 h /<6% 1.62–2.62/4–7 2.97306 [409] (2014)
Urea (P, 550 ◦ C) Air, 550 ◦ C, 2 h /8.0 16/ 2.86/151 [435] (2015)
MA (P, 550 ◦ C) Air, 500 ◦ C, 2 h 3.06/165.66 [436] (2014)
MA (P, 550 ◦ C) Air, 500 ◦ C, 2 h 5–8/10–20 2.91/122.6 [326] (2015)
MA (P, 520 + 540 ◦ C) Air, 540 ◦ C, 2 h /0.35% 2.93/210 [437] (2015)
MA (P, 500 + 520 ◦ C) Air, 520 ◦ C, 4 h 2.7/8 2.82/153.32 [438] (2016)
MA (P, 500 + 550 ◦ C) Air, 500 ◦ C, 2 h 1.9/6 2.97/150.1 [439] (2014)
MA (P, 600 ◦ C) Air, 500 ◦ C, 4 h 0.9/3 [440] (2015)
DCDA (P, 520 ◦ C) Air, 400 ◦ C, 4 h 2.89/ [441] (2013)
Commercial g-C3 N4 H2 , 400 ◦ C, 4 h 2/6 /260 [442] (2015)
(Carbodeon Ltd)
DCDA(P, 550 ◦ C) NH3 , 510 ◦ C, 1 h 20/50 2.95/196 [350] (2015)
Mixed DCDA/NH4 Cl Air, 550 ◦ C, 2 h 3.1/8 2.83/52.9 [443] (2014)
Mixed DCDA/NH4 Cl Air, 550 ◦ C, 4 h 1.0/3 2.77/77.7 [444] (2015)
Mixed MA/KCl Air, 550 ◦ C, 4 h 1.5–6.3 2.71/ [445] (2014)
Mixed MA/KBH4 Air, 550 ◦ C, 4 h 1.5/4 [446] (2014)
Guanidinium cyanurate Air, 550 ◦ C, 4 h 0.6–1.5/1–3 2.87/133.8 [447] (2015)
Guanidinium chloride Air, 600 ◦ C, 4 h 2.44/109.9 [448] (2014)
DCDA (P, 600 ◦ C) Air, 350 ◦ C, 2 h (NH4 Cl intercalation, N2 ) 2–3/6–9 2.85/30.1 [449] (2014)

Combined approaches
MA (P, 520 ◦ C) (Air, 550 ◦ C, 3 h)+ (isopropanol, 10/100, 8 h) 0.5/1 [450] (2014)
MA (P, 500 + 530 ◦ C) (Air, 550 ◦ C, 3 h)+ (methanol, 100/100, 4 h) 0.4–0.5/1 [451] (2014)
MA (P, 500 + 530 ◦ C) (Air, 550 ◦ C, 200 min)+ (methanol, 100/100, 4 h) 0.8–1.2/2–3 3.03/ [452] (2015)
MA (P, 520 ◦ C) (Air, 550 ◦ C, 3 h)+ (isopropanol, 8 h) 0.5/1 3.0/380 [453] (2014)
MA (P, 550 ◦ C) (Air, 550 ◦ C)+ (H2 SO4 + HNO3 , 100/40, 5 h) 2.95/109.30 [454] (2014)
MA (P, 520 ◦ C) (Air, 550 ◦ C, 3 h)+ (0.5 M HCl, 20/200, 8 h) 0.6/1 [455] (2015)
DCDA (P, 550 ◦ C) (H2 SO4 (98 wt%), 2000/50, 2 h) + (water, 1 h) 5–10/15–20 3.0/140 [456] (2015)
DCDA/2-aminobenzonitrile (P, (5 M HNO3 , 400/80, 20 h/under reflux)+ (water, 4 h) 0.6–4/2–10 2.89/ [457] (2016)
550 ◦ C)
Urea (P, 600 ◦ C) (H2 SO4 + HNO3 , 1000/200, 4 h)+ /10.5 [458] (2016)
(water, 30/30, 2 h)
◦
MA (P, 550 C) (75 wt% H2 SO4 , 300/30, 2 h 130 ◦ C) 2.5/7 2.88/80 [459] (2015)
+ (water + 300/200,2 h)
MA (P, 550 ◦ C) (H2 SO4 (98 wt%), 1000/10, 8 h) + (N2 , 550 ◦ C, 2 h) 0.8–1.4/3–4 2.79/54.3 [460] (2016)

Other approaches
MA (P, 550 ◦ C) Ball milling method /1–2 2.98/ [461] (2015)
MA and carbon fibre Microwave heating approach 1.6/5 2.88/239 [462] (2016)

P, pyrolysis (or thermal polycondensation); DMF, dimethylformamide.

 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 93

Fig. 31. (a) Schematic illustration for the synthesis process of ultrathin g-C3 N4 nanosheets via liquid exfoliation. (b) AFM image of the synthetic g-C3 N4 nanosheets. (d) The
corresponding height image of two random nanosheets [100].

employed to further achieve the 600 nm or near-infrared (NIR) pho-

tocatalysis of g-C3 N4 nanosheets in aqueous solution [52,476–478].

4.5. Surface sensitization

In general, there are five typical strategies to increase the visible-

light absorbance of wide band gap semiconductors: band-gap
engineering (impurity doping and solid solution), defect con-
trol, surface plasmon resonance (SPR) effect, sensitization by dye
and quantum dot [16]. Although the aforementioned two strate-
gies of band-gap engineering and defect control can partially
extend their visible-light absorption, the moderate band gaps
(∼2.7 eV) of g-C3 N4 -based semiconductors are still the main bottle-
necks affecting the highly effective generation of photo-generated
charge carriers, which thereby play the crucial roles in determin-
ing the visible-light photocatalytic performances of g-C3 N4 -based
semiconductors. Thus, other three strategies, including loading
Fig. 32. Schematic illustration for fabricting the ultrathin nanosheets of g-C3 N4
through a dicyandiamide-blowing method [443].
plasmonic metals, sensitization by quantum dots (QDs) and organic
dyes (the corresponding mechanisms shown in Fig. 33), have been
also widely applied in enhancing the visible-light absorbance of g-
milling [461] have also been successfully applied in obtaining 2D C3 N4 -based semiconductors, which will be thoroughly discussed
ultrathin C3 N4 nanosheets. More interestingly, the perfect com- in this section.
bination of liquid, chemical exfoliation and thermal oxidation Firstly, the famous SPR effects of noble metals, such as
etching could fully explore their potentials and achieve the low- Au [77,200,479–482] and Ag [433,455,479,483–492], have been
cost, simple, fast and scalable synthesis of 2D g-C3 N4 nanosheets widely employed to improve the visible-light absorbance and
[450,451,453,455,457,460], which deserves more attention in the charge separation of g-C3 N4 . In general, it is well accepted that
near future. the deposited plasmonic metals could function as electron sink,
In addition to developing new fabrication methods of g-C3 N4 reduction co-catalyst and photosensitizers to enhance the visible-
nanosheets, more efforts should be also devote to narrowing their light absorption of a given semiconductor [493]. For example, Bai
larger band gaps (0.1–0.2 eV higher than that of bulk g-C3 N4 ) and et al. fabricated the core–shell nanostructured Ag@C3 N4 photo-
promoting the fast utilization of photo-generated charge carriers catalysts through the simple methanol-reflux treatment of g-C3 N4
migrated to the surface of g-C3 N4 nanosheets. As effective strate- nanosheets deposited by Ag nanoparticles (as shown in Fig. 34)
gies, doping [84,118,128,328,471], introducing nitrogen vacancies [488]. The combination of LSPR effect of Ag nanoparticles and their
[347,472], sensitization [473], copolymerization [130,474,475] and hybrid effect with C3 N4 could achieve 1.8- and 30-time enhance-
hybridization with other semiconductors or co-catalysts could be ments in the photocatalytic MB degradation and H2 evolution,
94 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 33. Mechanisms for g-C3 N4 photocatalysts sensitized by (a) plasmonic metals, (b) quantum dots (QDs), (c) organic dyes.

H2 evolution under long-wavelength irradiation (>600 nm) [509].

The results indicated that the monolayer dye could achieve the
highest photocatalytic H2 -evolution performance due to promoted
charge generation, transfer and utilization, whereas excess thick-
ness of the dye layer will cover the co-catalyst sites, thus reducing
the photocatalytic activity [509]. Similarly, Lu and coworkers
successfully demonstrated that the sensitization of mesoporous
g-C3 N4 with a EY dye could achieve an H2 -evolution AQE of
19.4% under 550 nm irradiation [519]. It is suggested that the
high surface area and nanoporous structure of mpg-C3 N4 are
greatly favorable for deposition of EY molecules on its surface,
thus promoting the significantly increased and extended light
harvesting in the visible-light response region and further improv-
ing H2 -evolution activity. More surprisingly, Xu and coworkers
demonstrated that the deposition of ErB dye onto Pt/g-C3 N4 sam-
ple exhibited a remarkably enhanced H2 evolution rate (652.5 or
162.5 ␮mol h−1 ) from an aqueous solution of TEOA under visible
light irradiation (␭ > 420 nm or > 550 nm), with an AQY of 33.4%
at 460 nm [473]. The resulting ternary Pt/g-C3 N4 /ErB photocata-
lyst also showed the stability and good recyclability, remaining
90% of the activity after 5 runs [473]. Most recently, it has been
Fig. 34. Synthetic route and charge-separation mechanism for C3 N4 and core–shell demonstrated that the promising earth-abundant Co(OH)2 and
nanostructured Ag@C3 N4 photocatalysts under light irradiation [488]. MoS2 could be utilized as co-catalysts to boost the photocatlytic H2 -
evolution activity over these dye-sensitized g-C3 N4 photocatalysts
[517,520,521]. More interestingly, the g-C3 N4 -based photocatalytic
respectively. In another example, Wei et al. constructed the type-II systems co-sensitized by two organic dyes or inorganic photosen-
2D-1D C3 N4 /TiO2 hybrid nanofibers and further decorated plas- sitizers (plasmonic metals and QDs) are also highly desirable in
monic noble metal nanoparticles (Au, Ag, or Pt) with sizes from 5 future studies [510,512,521,522]. However, the apparent quantum
to 10 nm on them [479]. The resulting SPR sensitized heterostruc- effciency and stabilities of these systems are still needed to be fur-
tures could achieve highly efficient photocatalytic H2 evolution ther enhanced.
due to the simultaneous implementation of improved light absorp-
tion, charge separation and utilization. In future, it is expected that
the plasmonic alloys [494,495], Cu [496–498] and Bi [499–501] 4.6. Heterojunction construction
nanoparticles could be deposited onto g-C3 N4 to boost their visible-
light photocatalytic activity. Enhancing photocatalytic activity of g-C3 N4 -based semiconduc-
Secondly, the quantum dots modified g-C3 N4 photocatalytic tors could be also achieved through constructing semiconductor
systems are still very interesting and promising [502–505]. For heterojunctions, which could induce the band bending and the
example, Ge et al. first demonstrated that the deposition of 30 wt% formation of internal electrical field, thus significantly boosting
CdS QDs onto the bulk g-C3 N4 could achieve a 9-fold enhancement the efficient spatial charge separation [7]. In general, according
in the visible-light photocatalytic H2 -evolution activity, due to the to the semiconductors’ energy bands and Femi levels of metal
increased the absorbance of visible light and promoted charge sepa- co-catalysts, semiconductor heterojunctions can be divided into
ration [502]. Since then, CdS QDs have been widely used to improve four types: Schottky junction (Fig. 35A), Type I (Fig. 35B), Type
the visible-light activity of bulk g-C3 N4 for various kinds of appli- II (Fig. 35C) and Type III (Fig. 35D) heterojunctions. Clearly, only
cations [284,405,502,503,506–508]. In future, it is expected that Schottky junction and Type II heterojunctions can significantly
more efficient CdS/g-C3 N4 composite photocatalysts with earth- promote the fast spatial separation of electrons and holes, thus
abundant co-catalysts should be further exploited. retarding their recombination and prolonging their lifetime. Thus,
Thirdly, various kinds of low-cost organic dyes, such as magne- for photocatalysis, the construction of Schottky junction and Type
sium phthalocyanine (MgPc) [509], zinc phthalocyanine [510–515], II alignment should be highly desired. The Schottky junction will
Xanthene [516], Erythrosin B (ErB) [473,517] and Eosin Y (EY) [518], be discussed in the next section. Here, we will focus on the Type
have been readily coupled with different nanostructured g-C3 N4 II g-C3 N4 -based heterojunctions. As observed the CB and VB lev-
to fabricate the highly efficient organic semiconductor heterojunc- els of different semiconductors in Table 1 and Fig. 16, it is easily
tions. For example, Domen and his coworkers deposited an organic found that several commonly used semiconductors, such as TiO2
MgPc dye (with a band gap of 1.8 eV) on the Pt/mpg-C3 N4 com- [523], Cu2 O [524–526], ZnO [291,527–537], WO3 [286,538–544],
posite semiconductors and achieve the enhanced photocatalytic BiVO4 [545–551], (BiO)2 CO3 [552], Ag3 PO4 [553–560], CdS
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 95

Fig. 35. Spatial charge-separation mechanisms for four different types of semiconductor heterojunctions: (A) Schottky junction, (B) Type I, (C) Type II, and (D) Type III
heterojunctions.

[197,284,405,502,503,506,508,561–566], BiOX [567–575], Bi2 WO6 leading to the strong redox ability and enhanced photocataly-
[552,576–583], Fe2 O3 [115,289,584–587] and different types of g- sis [593]. In nature, photosynthesis of plants generally proceeds
C3 N4 [121,588] can be combined with g-C3 N4 to construct the Type according to the so-called Z-scheme photocatalytic process, in
II heterojunctions and achieve the efficient charge separation. Here, which two isolated reactions of water oxidation and CO2 reduction
the CdS/g-C3 N4 and the g-C3 N4 isotype heterojunctions will be are linked together through the redox mediators [593]. Mimicking
discussed. the natural photosynthesis process, the artificial Z-scheme semi-
Besides the above mentioned systems of CdS quantum conductor heterojunctions have been successfully proposed and
dots/g-C3 N4 [502,503,561], various kinds of other nanostruc- constructed by combining two different semiconductors through
tured combinations, such as core/shell CdS@g-C3 N4 Nanowires liquid-state or all-solid-state mediators. Each semiconductor in
[284,562], g-C3 N4 /Au/CdS Z-scheme [589,590], CdS nanopar- the Z-scheme is only responsible for one (oxidation or reduc-
ticles/2D g-C3 N4 nanosheets [563] and CdS nanorods/g-C3 N4 tion) reaction, thus achieving the extremely extended visible-light
nanosheets [197,562,591,592] have been also successfully con- absorption, strengthened redox ability, improved photostability,
structed to obtain the highly efficient and stable composite charge-separation and photocatalytic efficiency [594,595]. In this
photocatalysts. Among them, the core/shell heterojunctions seem regard, the all-solid-state g-C3 N4 -based Z-scheme photocatalytic
to be more promising, due to the suppressed CdS photocorrosion systems seem to exhibit many advantages and great potential
and the optimized intimate interface contact. For example, Zhang in practical applications in photocatalytic fields. Commonly, the
et al. demonstrated that the as-constructed novel CdS/2 wt% g- artificial heterogeneous all-solid-state g-C3 N4 -based Z-scheme
C3 N4 core/shell nanowires could achieve an optimal photocatalytic photocatalytic systems could overcome the weak oxidation ability
activity of up to 4152 ␮mol h−1 g−1 [562]. It is believed that the and decrease the reduction capacity of single-g-C3 N4 and g-C3 N4 -
well-matched Type II g-C3 N4 /CdS heterojunctions could achieve based heterojunctions, respectively, and simultaneously fulfill a
the positive synergic effect of accelerating the separation of charge wide absorption range, long-term stability, high charge-separation
carriers and inhibiting the CdS corrosion (as shown in Fig. 36a), thus efficiency and strong redox ability [523,596,597].
greatly enhancing the photocatalytic activity and photostability Typically, two kinds of all-solid-state g-C3 N4 -based Z-scheme
[562]. Interestingly, based on the slight difference in their elec- photocatalytic systems with and without mediators are displayed
tronic band structures (Fig. 36b), Wang and coworkers et al. firstly in Fig. 37a and b, respectively. For the rational design of these
demonstrated that the as-prepared Type II isotype heterojunctions two kinds of all-solid-state g-C3 N4 -based Z-scheme photocatalytic
of g-C3 N4 /S-mediated g-C3 N4 (S-g-C3 N4 ) exhibited the matched systems, the achievement of the intimate Ohmic contact should
band gaps and efficiently promoted charge separation of the band be the most important point, which could be obtained through
offsets (Fig. 36b), thus significantly enhancing photocatalytic activ- introducing the conductors, such as conductive carbon and met-
ity for H2 evolution [121]. The isotype heterostructure is similar to als, or fabricating the perfect interfacial contact. For example, Yu
that of phase junction in the formation mechanism, which provides and coworkers, for the first time, constructed a direct g-C3 N4 –TiO2
new opportunities to construct buried layered junctions in the Z-scheme photocatalyst without an electron mediator by a facile
various copolymerized g-C3 N4 -based composites with improved calcination route, which could achieve the intimate interfacial
charge photon-excitation and charge separation [54]. Similarly, contact [523]. The results showed that the as-prepared Z-scheme
Dong and coworkers in situ constructed a novel Type II layered photocatalysts was highly dependent on the g-C3 N4 content. Ide-
g-C3 N4 /g-C3 N4 metal-free isotype heterojunction with enhanced ally, the surface of the TiO2 nanoparticles should be partially
photocatalytic activity for the removal of NO in air [588]. The results covered by the g-C3 N4 nanoparticles, which are favorable for the
further confirmed the key roles of the Type II isotype heterojunc- formation of a g-C3 N4 -TiO2 Z-scheme photocatalytic system (see
tion in achieving the efficient charge separation and transfer across Fig. 38a and b). In contrary, the excessively high contents of g-
the heterojunction interface as well as prolonged lifetime of charge C3 N4 can not only lead to the complete cover of TiO2 surface,
carriers. which could decrease the charge carrier excitation of TiO2 , but also
As observed in Figs. 35 b and 36, for the favorable Type II het- increase the recombination rate of photo-generated electrons and
erojunction systems, the photocatalytic redox reactions mainly holes on g-C3 N4 (see Fig. 38c). Similar Z-scheme systems between
occur on the surface of semiconductor with lower CB and VB g-C3 N4 and TiO2 have also been observed in other reports [598,599].
edges, implying the weaker reduction and oxidation ability (driving Some other direct g-C3 N4 -based Z-scheme photocatalysts, such as
forces) in this kind of heterojunction-type photocatalytic system. Bi2 O3 /g-C3 N4 [600], ZnO/g-C3 N4 [601,602], BiVO4 /g-C3 N4 [603],
In contrary, as observed in Fig. 37, for the all-solid-state Z-scheme g-C3 N4 /Bi2 MoO6 [604], WO3 /g-C3 N4 [605,606], g-C3 N4 /Ag3 PO4
photocatalytic system with the Ohmic-contact interfaces, their [607–609], BiOCl-g-C3 N4 [610], Bi2 WO6 /g-C3 N4 [505] have also
photocatalytic activities are majorly dependent on the surface been available. Additionally, some typical electron mediators,
properties of semiconductor with higher CB and VB edges, thus such as nanocarbon [611], Au [590,612], RGO [613] and Bi [614]
96 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 36. Schematic illustration of spatial charge separation in CdS/g-C3 N4 (a) and g-C3 N4 /S-g-C3 N4 (b).

Fig. 37. Schematic illustration of spatial charge separation in the all-solid-state g-C3 N4 -based Z-scheme photocatalytic systems with (a) and without (b) mediators.

Fig. 38. Schematic illustration for the charge transfer and separation in g-C3 N4 -TiO2 Z-scheme photocatalysts under UV light irradiation [523].

could be used to construct the indirect g-C3 N4 -based Z-scheme More importantly, the direct or indirect experimental evidence
photocatalysts. In future, improvements in the morphology of for supporting the proposed Z-scheme charge-transfer mechanism
semiconductors and interfacial coupling should be deeply and con- should be provided as far as possible. In fact, the technologies such
tinually investigated to search for highly effective g-C3 N4 -based as radicals (• O2 − and • OH) trapping experiments, metal deposition
Z-scheme photocatalysts for practical applications [598,615–618]. and double-beam photoacoustic (DB-PA) spectroscopy have been
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 97

be further enhanced through improving the tightness of interfaces

and introducing the interfacial mediator [476,638].

4.7. Co-catalyst loading

The level of the conduction bands of g-C3 N4 is −1.3 V (vs.

NHE), which is more negative than the reduction potentials
•
of CO2 /CO(−0.51 V), H + /H2 (0.41 V), and O2 /O2 − (0.33 V),
respectively (As shown in Fig. 41). Thermodynamically, the photo-
generated electrons on the CB of g-C3 N4 have much stronger
driving force (or over-potentials) for these three typical kinds of
reduction reactions, as compared to those in TiO2 [28,657,658].
However, the obvious structure defects in bulk g-C3 N4 generally
lead to their fast recombination with the photo-excited holes.
More importantly, the photocatalytic H2 evolution and CO2 reduc-
Fig. 39. Schematic illustration of 2D layered composites in comparison with other tion are typical up-hill reactions, thus resulting in the sluggish
kinds of composites [476].
kinetics on the surface of bulk g-C3 N4 . Fortunately, these disad-
vantageous factors could be simultaneously overcome by loading
employed to reveal the real Z-scheme charge-transfer mechanism suitable reduction co-catalysts onto the surface of g-C3 N4 , which
[523,534,601,608,619,620]. could lower the reaction activation energy (or electrochemical
In addition, it should be also noted that the interfacial con- overpotentials), improve the charge separation and transport,
tact/coupling performances could be further improved by several increase stability of photocatalyts, and accelerate the sluggish reac-
strategies, such as, increasing the contact areas, improving the tion kinetics of various surface reduction reactions, thus greatly
tightness of interfaces [621–624] and introducing the highly- enhancing the photocatlytic activity [88,124]. Essentially speak-
conductive interfacial mediator [625–627]. Clearly, larger contact ing, the single-electron or multi-electron O2 -reduction reactions
area can provide sufficient charge transfer and trapping chan- (as shown in Table 2) are of significant importance for photocat-
nels for achieving their fast separation. As compared with other alytic degradation [83,410,657], selective organic transformations
types of composite pohotocatalysts with 1D (i.e. 0D/1D and [119,244] and disinfection [659,660]. More interestingly, the co-
1D/1D) or 2D (i.e. 0D/2D and 1D/2D) contact interfaces, the catalysts can also achieve the selective photoreduction products
unique 2D–2D layered nano-junctions possess the much larger of CO2 [16,661]. In addition, it is also necessary to deposit suit-
contact surface between the two adjacent sheets (as shown in able hole co-catalysts to accelerate the difficult water oxidation
Fig. 39), thus favoring more efficient interfacial charge separa- reactions, due to the lower overpotential of g-C3 N4 for water oxi-
tion and photo-activity enhancement [476]. More fortunately, dation (0.59 V), as well as the inherent challenges of four-electron
g-C3 N4 itself possesses a unique 2D layered structure, which holds water oxidation [7,662]. Thus, it is obvious that all these reduc-
great promise for potential applications in constructing 2D layered tion and oxidation co-catalysts play decisive roles in achieving
composite photocatalysts. In 2011, Xiang et al. first constructed highly efficient and selective photocatalytic reactions. These four
graphene/g-C3 N4 composite photocatalysts with the larger 2D-2D types of co-catalysts over g-C3 N4 (as shown in Fig. 41), namely,
coupling interfaces (as shown in Fig. 40a) [151], demonstrating a H2 -evolution, CO2 -reduction, O2 -reduction and H2 O-oxidation co-
more than 3.07-time enhancement of photocatalytic H2 -evolution catalysts, are summarized in Table 6, which will be compared and
activity (using Pt and methanol as cocatalyst and sacrificial discussed in this section in detail.
agent, respectively). Subsequently, a series of 2D g-C3 N4 -based Similar to those co-catalysts on TiO2 [25], these different co-
layered heterojunctions (e.g. MoS2 [120,290,292,628–633], SnS2 catalysts over g-C3 N4 -based photocatalysts can be divided into
[634–636], WS2 [637,638], graphene [482,639], SnNb2 O6 [640], three categories (as shown in Table 6): noble-metal co-catalysts,
WO3 [287], BiOBr [641], layered double hydroxide [288,642,643], earth-abundant metal co-catalysts, metal-free and hybrid co-
Bi4 O5 I2 [644] and Bi2 O2 CO3 [645]) have been widely fabricated for catalysts (nano carbons). The nano carbons as co-catalysts will
different photocatalytic applications. Among them, g-C3 N4 /MoS2 be highlighted in the next section. Here, we will focus on the
2D-2D coupling systems have attracted much attention since the noble-metal and earth-abundant metal co-catalysts, especially for
first report about concept of layered nanojunctions by Hou et al. in the latter. As observed from Table 5, it is clear that the more
2003 (as shown in Fig. 40b) [120]. It is believed that 2D layered MoS2 efforts have been devoted to the developments of H2 -evolution
can function as co-catalysts [646], stable semiconductor sensitizers and O2 -reduction co-catalysts. On the one hand, the noble-metal
[647] or electron trapper [648,649] in these systems. More inter- co-catalysts (e.g., single-atom [664], bimetallic [193,194,481] and
estingly, the layered triple-nanojunctions in the ternary g-C3 N4 co-loading [200,668]) seem to be more promising for both photo-
nanosheets/N-doped graphene/MoS2 have also been successfully catalytic H2 -evolution and O2 -reduction reactions, which deserve
fabricated, which has been shown to significantly improve the pho- more attention in the future studies. On the other hand, for earth-
tocatalytic activity of MB oxidation and Cr(VI) reduction through abundant metal co-catalysts, the 2D layered co-catalysts, such
the synergistic effects of multiple 2D-2D coupling interfaces [650]. as MoS2 [292,328,517,599,628–630,632,735], Ni(OH)2 [126,669],
These results highlighted that the unique 2D–2D layered nano- WS2 [637,638], Cu(OH)2 [521], and NiSx [125,197,670–673], have
junctions with larger contact area are more promising for the fast become the shinning stars in the fields of photocatalytic H2
separation of photo-excited charge carriers across the interfaces generation and degradation of pollutants (for O2 reduction),
with respect to the 0D–2D and 1D–2D coupling systems. More which will be still the prescriptive research topics in these
interestingly, the coupling of g-C3 N4 nanosheets and semiconduc- fields. In addition, the fabrication of nanostructured hybrid co-
tor nanosheets with exposed facets seems to be more promising catalysts [155,156,198,651,678] and development of molecular
in various kinds of photocatalytic applications, due to the diver- clusters (such as Fe(III)/Co(III) [245,736,758]) and amorphous co-
sified synergy effects [418,427,559,572,641,651–656]. In future, it catalysts[759] might become an attractive direction in the near
is expected that the 2D–2D interface coupling performances could future.
98 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Table 6
Summary of various kinds of co-catalysts over g-C3 N4 -based photocatalysts.

Roles/functions of co-catalysts Noble-metal co-catalysts Earth-abundant metal co-catalysts Metal-free and Hybrid co-catalysts
(nano carbons)

H2 evolution Metal: Pt [663], single-atom Pt Ni(OH)2 [126,669], WS2 [637,638], Graphene [151], carbon black/NiS
[664] Cu(OH)2 [521], MoS2 [156], carbon QDs [680], CNTs
Sulfides: Ag2 S [665] [328,517,628,632], NiSx [681], CNTs/NiS [198], C60, carbon
Plasmonic: Au [666,667], Ag [125,197,670–673], NiOx , Cu [674], fiber [682], ZIF-8 derived carbon
[479,488] Ni [675,676], Ni(dmgH) 2 [677], [683], acetylene black/Ni(OH)2 [155]
Bimetallic: PtCo [193], AuPd [194] hollow Zn0.30 Co2.70 S4 [678], [Ni
Co-loading: Au/Pt [668], Au/PtO (TEOA)2 ]Cl2 [679], Co0.04 Mo0.96 S2
[200] [651]
Hole co-catalysts RuO2 , [44,133] CoOx [285,684], Co(OH)2 [685], Graphene/LDH [288]
layered double hydroxide (LDH)
[288,686] Co(II) ions [687], Co3 O4
[688,689], Co-Pi [690]
CO2 reduction Pt [691–693], single-atom (Pd/Pt) Layered double hydroxide [642] Phosphate [701], graphene
[694], ruthenium complex [160,702–704], carbon [705], CNTs
[695–700] [706], S-doped porous carbon
[707], UiO-66 (zirconium-based
MOFs) [708], Co-ZIF-9
(cobalt-based MOFs)[709]
O2 reduction (degradation) Pt, Au [590], Ag NiO [734], MoS2 Graphene [220,244,739–744],
[433,483,485,488,506,710–723], [292,599,629,630,735], Fe(III) carbon QDs [745,746], CNTs [747],
Ag2 O [724–728], Pd [729–732], [736], H3 BO3 [737], Phosphate biochar [748], PANI [749–751], C60
bimetallic Au/Pt [481], Ag [738,739], Fe (III)/Co(III) [245] [752,753] graphene/Ag [710,754],
Quantum Cluster[733] CNTs/Au [755], ordered
mesoporous carbon [756,757]

Relatively speaking, there are only limited reports about plex [760,761], Nocera cobalt phosphate (CoPi) [762,763], IrO2
the photocatalytic water oxidation over g-C3 N4 -based pho- [764], NiOx [765–767], or g-C3 N4 /graphene [262], should be paid
tocatalysts modified by Co-based molecules or compounds, more attention in future studies. Similarly, so far, only few co-
[285,684,685,687–689] RuO2 [44,133] or LDH [288,686]. In this catalysts on g-C3 N4 , e.g., Pt-based, [691–694] ruthenium complex
regard, other water-oxidation co-catalysts such as cubic Co com- [695–700], LDH [642], Phosphate [701], MOFs [708,709] and car-

Fig. 40. Schematic illustration of 2D-2D coupling of g-C3 N4 /graphene (a) and g-C3 N4 /MoS2 (b).

Fig. 41. Four kinds of co-catalysts over g-C3 N4 .

 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 99

Fig. 42. Roles of carbon materials in enhancing the performance of g-C3 N4 -based
composite photocatalysts [781].

bon [160,702–707], have been available for selective photocatalytic

CO2 reduction. Thus, in future, it is expected that more and more
earth-abundant CO2 -reduction co-catalysts with high activity and
selectivity could be developed and utilized in the production of
solar fuels from the CO2 photoreduction.

4.8. Nanocarbon loading Fig. 43. The proposed mechanism for photocatalytic water splitting over the g-
C3 N4 (electron sink and H2 -evolution site)/RGO-3 composite [773].

So far, various kinds of carbon materials,

including CNTs [147,198,747,755,768], graphene Most importantly, a higher O concentration could achieve a type-II,
[151,160,288,650,702,703,769–773], C60 [752,753], carbon quan- staggered band alignment at the g-C3 N4 -RGO interface, leading to
tum dots [745,774–777], carbon fibers [682], activated carbon, the high hydrogen-evolution activity over O atoms (as active sites)
carbon black [156,778,779], acetylene black [155], etc. have been in the RGO (Fig. 43) [773]. The findings pave the way for develop-
widely coupled with g-C3 N4 to fabricated the g-C3 N4 /carbon ing RGO-based composites for photocatalytic applications. At this
hybrid materials [780]. The essential reasons can be attributed to point, the semiconductor properties of RGO are more promising
the promoted charge separation by the as-formed carbon-based in constructing composite photocatalysts [740], which deserves
Schottky-junction between g-C3 N4 and the highly conductive more attention in future studies. In addition, doping or co-doping
nano carbon materials and the enhanced adsorption performances of RGO materials with heteroatoms has also been demonstrated
from narrowing band gap due to the carbon doping [25]. More to exhibit the significantly enhanced electrocatalytic performances
specifically, coupling with various carbon rich materials with [791], which are also highly expected to be utilized in constructing
g-C3 N4 not only compensate the disadvantages of individual g-C3 N4 /doped RGO composite photocatalysts.
semiconductor materials, but also induce the interesting syner-
getic effects, like supporting material, increasing adsorption and 5. Potential applications of g-C3 N4 -based composite
active sites, electron acceptor and transport channel, cocatalyst, photocatalysts
photosensitization, photocatalyst, and band gap narrowing effect
(as shown in Fig. 42) [781]. Here, we will highlight the hybrids of 5.1. Photocatalytic water splitting
g-C3 N4 /graphene, which have been the most widely investigated
g-C3 N4 /carbon composite photocatalysts. Since the pioneering works by Honda and Fujishima in 1972 [1],
Compared to the 0D and 1D carbon materials, graphene, a various heterogeneous photocatalysts have been widely applied
sp2 -hybridized 2D carbon nanosheet, exhibits a much higher in the attracted photocatalytic hydrogen production from water
optical transmittance, conductivity (∼5000 W m−1 K−1 ), electron reduction [7]. Normally, photocatalytic water splitting systems
mobility (200,000 cm2 V−1 s−1 ), theoretical specific surface area can be divided into half-reaction water splitting (for H2 and O2 )
(∼2600 m2 g−1 ) and more suitable work function (4.42 eV) for H2 and overall water splitting systems [7]. Interestingly, g-C3 N4 has
evolution [17,658,782–787]. Thus, the combination of g-C3 N4 and been extensively applied in these two systems to boost their pho-
graphene has been widely shown to be one of promising strategies tocatalytic activity for water splitting. Table 7 summarizes the
to favor the charge transfer and inhibit the charge recombination photocatalytic activities of g-C3 N4 based photocatalysts for H2
process, thereby leading to an enhanced photocatalytic activity for generation on various conditions, including the amount of pho-
H2 production. As displayed in Fig. 40a, the 2D-2D coupling inter- tocatalysts, the sacrificial reagents, H2 generation rate, and the
face in the g-C3 N4 /graphene hybrids could achieve much larger corresponding quantum efficiency in this review. As shown in
interfacial coupling areas and more efficient charge separation, as Table 7, co-catalysts and sacrificial reagents are crucial for achiev-
compared to the 0D-2D and 1D-2D hybrids. For example, the dop- ing the highly efficient photocatalytic H2 evolution, which will be
ing of g-C3 N4 by graphene could be achieved through formation discussed in detail.
of C O C covalent bonding or ␲-␲ stacking interactions, both of As observed in Table 7, it is clear that the high H2 -evolution
which can effectively narrow the band gap of g-C3 N4 , thus leading activity over nanostructured g-C3 N4 -based semiconductors is gen-
to the enhanced visible-light photocatalytic activity [702,788–790]. erally obtained via loading the shape-dependent noble-metal Pt
Recently, based on the state-of-the-art hybrid DFT, Xu et al. system- nanoparticles as co-catalysts [315,321,348,445,562,809,819,823].
atically investigated the interaction between the g-C3 N4 and RGO In the pioneering work, Wang and co-workers found that the
sheets [773]. It was demonstrated that the appropriate O concen- loading 3 wt% Pt as co-catalysts on g-C3 N4 could achieve the H2 -
tration plays a crucial role in altering the direct gap to indirect one. evolvtion amount of 770 ␮mol after 72 h in the TEOA aqueous
 100
Table 7
Summary of the photocatalytic H2 evolution on g-C3 N4 -based photocatalysts.

photocatalyst structure synthetic method co-catal./mass ratio mass (g) light source incident light aqueous co- QY (%) reference
reaction catal./activity (year)
(␮mol h−1 )

Ni@/g-C3 N4 particles/lamellar solvothermal method Ni/10 wt.% 0.05 500 W Xe lamp quartz reactor 10 vol.% TEOA Ni/8.41 [192] (2015)
NiS/g-C3 N4 nanoparticles/lamellar hydrothermal method NiS/1.25 wt.% 0.1 300 W Xe lamp, Pyrex reactor 15 vol.% TEOA NiS/46 1.9 (440 nm) [125] (2013)
␭ > 420 nm
NiS/g-C3 N4 nanoparticles/lamellar in stiu ion-exchange method NiS/1.5 mol% 0.1 300 W Xe lamp, 10 vol.% TEOA NiS/44.77 [670] (2014)
␭ > 420 nm
NiS/e-C3 N4 ultrathin liquid NiS/1.0 wt.% 0.05 150 W Xe lamp, quartz reactor 10 vol.% TEOA NiS/4.2 [671] (2015)
nanosheets/nanoparticles exfoliation-hydrothermal ␭ > 400 nm
method
Ni(OH)2 /g- nanoparticles/lamellar precipitation method Ni(OH)2 /0.5 wt.% 0.05 350 W Xe arc lamp, Pyrex reactor 10 vol.% TEOA Ni(OH)2 /7.6 1.1 (420 nm) [126] (2013)
C3 N4 ␭ > 400 nm
Ni/NiO/g-C3 N4 core-shell/lamellar in situ immersion method Ni/NiO/2 wt.% 0.05 350 W Xe lamp, Pyrex reactor 10 vol.% TEOA Ni/NiO/10 [792] (2015)
␭ > 420 nm
NiS/CNT/mpg- nanoparticles/nanotubes/lamellar
sol-gel-precipitation method NiS/1 wt.% 0.05 300 W Xe lamp, quartz reactor 10 vol.% TEOA NiS/26.05 [198] (2015)
C3 N4 ␭ ≥ 420 nm
NiS/CB/g-C3 N4 nanoparticles/lamellar physical mixing-chemical CB/0.5 wt.%, 0.05 300 W Xe lamp, quartz reactor 15 vol.% TEOA CB, NiS/49.6 [156] (2015)

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

deposition NiS/1.0 wt.% ␭ ≥ 420 nm
Ni(dmgH)2 /g- sub-mircowires/lamellar chemical deposition Ni(dmgH)2 /3.5 wt.% 0.005 300 W Xe lamp, quartz reactor 15 vol.% TEOA Ni(dmgH)2 /1.18 [677] (2014)
C3 N4 ␭ > 420 nm
g-C3 N4 ultrathin nanosheets co-polymerization-surface Pt/3 wt.% 0.05 300 W Xe arc lamp, Pyrex reactor 10 vol.% TEOA Pt/28.55 [793] (2016)
activation-exfoliation ␭ > 420 nm
pm-g-C3 N4 porous sintering Pt/3 wt.% 0.1 300 W Xe lamp, 10 vol.% TEOA Pt/41.7 [159] (2017)
␭ > 420 nm
g-C3 N4 microsphere solvothermal method Pt/3 wt.% 300 W Xe lamp, 15 vol.% TEOA Pt/1.80 1.62 (420 nm) [397] (2015)
␭ > 420 nm
g-C3 N4 lamellar heating acetic acid treat Pt/1 wt.% 0.1 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/34 [794]
melamine ␭ > 420 nm (2015)
g-C3 N4 flower-like nanorods recrystallization method Pt/3 wt.% 0.05 300 W Xe lamp, quartz reactor 10 vol.% TEOA Pt/261.8 [795]
␭ > 420 nm (2015)
quasi-2D-C3 N4 lamellar melamine-assisted exfoliation Pt/0.6 wt.% 0.1 300 W Xe lamp, 10 vol.% TEOA Pt/89.28 [428] (2015)
method ␭ > 420 nm
mg-C3 N4 mesoporous calcinating-dissolving method Pt/3 wt.% 0.05 300 W xenon lamp, Pyrex reactor 10 vol.% TEOA Pt/272 [796] (2015)
␭ > 400 nm
CNIC nanotubes molten salt Pt/3 wt.% 0.1 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/502 21.2 (420 nm) [106] (2013)
␭ > 420 nm
CNT/g-C3 N4 nanotubes/lamellar calcinating method CNT/2 wt.%, Pt/1.2 wt.% 0.1 300 W Xe arc lamp, 10 vol.% TEOA Pt/39.4 [147] (2014)
␭ > 420 nm
MVNTs/g-C3 N4 nanotubes/particles calcinating method MVNTs/2.0 wt.% 0.1 300 W Xe arc lamp, quartz reactor 25 vol.% CH3 OH MVNTs/1.15 [681] (2012)
␭ > 400 nm
C/g-C3 N4 fiber/lamellar electrospinning and Pt/1.0 wt.% 0.05 350 W Xe arc lamp, Pyrex reactor 10 vol.% TEOA Pt/54 [682] (2015)
calcinations method ␭ > 420 nm
C/g-C3 N4 nanoparticles/rectangular molten salt method carbon black/0.5 wt.%, 0.1 visible light, ␭ > 420 nm quartz reactor 25 vol.% CH3 OH C, Pt/69.8 [779] (2014)
nanotube Pt/3 wt.%
C-dots/g-C3 N4 dots/lamellar mixing-calcinating method C-dots/0.25 wt.% 0.05 4 × UV-LEDs (3 W, Pyrex reactor 25 vol.% CH3 OH 8.6 [797] (2015)
␭ = 420 nm)
CQDs/g-C3 N4 quantum dots/lamellar hydrothermal method CQDs, Pt/3 wt.% 0.05 400 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/5.805 [680] (2016)
␭ > 420 nm
C-dots/g-C3 N4 nanodots/ultrathin hydrothermal method C-dots/0.2 wt.%, 0.05 300 W Xe lamp, 5 vol.% CH3 OH Pt/88.1 [777]
nanosheets Pt/0.2 wt.% ␭ > 420 nm (2016)
C-ZIF/g-C3 N4 nanoparticles/lamellar thermal condensation C-ZIF/1 wt.% 0.1 300 W Xe lamp, 0 vol.% TEOA C-ZIF/32.58 [683] (2016)
␭ > 400 nm
N/g-C3 N4 nanosheet calcinating method N-doped,Pt/3 wt.% 0.05 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/64 [798] (2016)
␭ > 420 nm
C3 N4+x lamellar co-thermal condensation N-doped,Pt/3 wt.% 0.08 300 W Xe lamp, 10 vol.% TEOA Pt/44.28 [799] (2015)
␭ > 400 nm
Table 7 (Continued)

photocatalyst structure synthetic method co-catal./mass ratio mass (g) light source incident light aqueous co- QY (%) reference
reaction catal./activity (year)
(␮mol h−1 )

P/g-C3 N4 flowers of in-plane calcinating method P-doped, Pt/3 wt.% 0.05 300 W Xe arc lamp, Pyrex reactor 10 vol.% TEOA Pt/104.1 [315] (2015)
mespores ␭ > 400 nm
P/g-C3 N4 lamellar copolymerization P-doped 0.1 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/50.6 [324]
␭ > 420 nm (2015)
Br/g-C3 N4 lamellar calcinating method Br-doped, Pt/3 wt.% 300 W Xe lamp, 10 vol.% TEOA Pt/48 [800] (2016)
␭ ≥ 420 nm
g-C3 N4 nanosheets have a porous calcinating method O-doped, Pt/3 wt.% 0.05 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/60.2 7.8 (420 nm) [321] (2015)
network ␭ > 420 nm
S/g-C3 N4 lamellar calcinating method S-doped, Pt/1 wt.% 0.1 300 W Xe arc lamp, quartz reactor 25 vol.% CH3 OH Pt/12.16 [307] (2013)
␭ > 400 nm
K-g-C3 N4 lamellar KCl-template method K, Pt/0.5 wt.% 0.01 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/102.8 [445] (2014)
␭ > 420 nm
Zn/g-C3 N4 lamellar calcinating method Zn-doped, Pt/0.5 wt.% 0.2 200 W Xe arc lamp, Pyrex reactor 18.5 vol.% Pt/59.5 3.2 (420 nm) [300] (2011)
␭ ≥ 420 nm CH3 OH
Co-Pi/g-C3 N4 nanoparticles/aggregated in situ photodepositions Co–Pi, Pt/1 wt.% 0.1 300 W Xe arc lamp, quartz reactor 25 vol.% CH3 OH Pt/19.48 [690] (2013)
␭ > 400 nm

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

sheets 0.05 M AgNO3
Au/g-C3 N4 nanoparticles/lamellar deposition-precipitation Au/1 wt.% 0.02 125 W Hg lamp, 10 vol.% TEOA Au/177.4 [666] (2014)
method ␭ > 400 nm
AuPd/g-C3 N4 nanoparticles/lamellar chemical reduction-calcinating AuPd/0.5 wt.% 0.05 300 W Xe arc lamp, quartz reactor 10 vol.% TEOA AuPd/16.3 [194] (2015)
method ␭ ≥ 400 nm
Pt-Au@ g-C3 N4 lamellar photodeposition method Pt, Au 0.08 300 W Xe lamp, Pyrex reactor 6.2 vol.% TEOA Pt-Au/17 [350] (2015)
␭ > 420 nm
Au/PtO/g-C3 N4 nanoparticles/lamellar photodeposition method Au/0.33 wt.%, 0.05 300 W Xe arc lamp, Pyrex reactor 25 vol.% CH3 OH Au/PtO/16.9 [200] (2016)
Pt/0.40 wt.% ␭ > 400 nm
CsTaWO6 /Au/g- gathered impregnaton method Au/0.5 wt.% 0.05 300 W Xe lamp, quartz reactor 20 vol.% CH3 OH Au/0.458 [667] (2015)
C3 N4 block/nanoparticles/lamellar
Cd0.5 Zn0.5 S/g- nanoparticles/lamellar hydrothermal method 0.1 Xe lamp, ␭ > 420 nm Pyrex reactor 0.35 M Na2 S 20.8 mL/h 37 (425 nm) [801] (2015)
C3 N4 and 0.25 M
Na2 SO3
Cd0.2 Zn0.8 S/g- nanoparticles/lamellar hydrothermal method 0.05 300 W Xe lamp, Pyrex reactor 0.1 M Na2 S and 208.8 [802]
C3 N4 ␭ > 420 nm 0.1 M Na2 SO3 (2015)
CdLa2 S4 /mpg- particles/lamellar hydrothermal method 0.05 300 W Xe lamp, quartz reactor 0.1 M Na2 S and 299.24 7.1 (420 nm) [803]
C3 N4 ␭ > 420 nm 0.5 M Na2 SO3 (2016)
CdS QDs/lamellar in situ hydrothermal method Pt/0.5 wt.% 0.005 300 W Xe lamp, quartz reactor 0.1 M Pt/22.47 8 (420 nm) [503] (2013)
QDs/g-C3 N4 ␭ > 420 nm L-ascorbic acid
CdS QDs/lamellar chemical impregnation Pt/1.0 wt.% 0.1 300 W Xe lamp, quartz reactor 25% vol.% Pt/17.27 [502] (2012)
QDs/g-C3 N4 method ␭ > 400 nm CH3 OH
CdS QDs/hollow Pt/3 wt.% 0.02 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/601 [804] (2015)
QDs/g-C3 N4 ␭ > 420 nm
g-C3 N4 /CdS particles/particles in situ self-transformation Pt/1.0 wt.% 0.05 350 W Xe arc lamp, Pyrex reactor 0.35 M Na2 S Pt/265.15 3.16 (420 nm) [348] (2015)
method ␭≥420 nm and 0.25 M
Na2 SO3
CdS/g-C3 N4 core/cell nanowires solvothermal-chemisorption Pt/0.6 wt.% 0.05 350 W Xe arc lamp, Pyrex reactor 0.35 M Na2 S Pt/207.6 4.3 (420 nm) [562] (2013)
method ␭≥420 nm and 0.25 M
Na2 SO3
NiS/CdS/g- nanoparticles/nanorodes/lamellar
in situ hydrothermal method NiS/9 wt.% 0.05 300 W Xe lamp, quartz reactor 10 vol.% TEOA NiS/128.2 [197] (2015)
C3 N4 ␭≥420 nm
Ni(OH)2 /CdS/g- core/shell nanorodes hydrothermal method Ni(OH)2 /4.76 0.001 300 W Xe lamp, quartz reactor 0.25 M Na2 S Ni(OH)2 /115.18 16.7 [669]
C3 N4 ␭ > 420 nm and 0.35 M (450 nm) (2016)
Na2 SO3
MoS2 /g-C3 N4 flower-like/lamellar in situ light-assisted method MoS2 /2.89 wt.% 0.01 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA MoS2 /2.52 [632] (2015)
␭ > 400 nm
MoS2 /g-C3 N4 nanoparticles/lamellar mixing-calcinating method MoS2 /0.5 wt.%, 0.1 300 W Xe arc lamp, quartz reactor 25 vol.% CH3 OH MoS2 , Pt/23.1 [628] (2013)
Pt/1.0 wt.% ␭ > 400 nm

101
Table 7 (Continued)

102
photocatalyst structure synthetic method co-catal./mass ratio mass (g) light source incident light aqueous co- QY (%) reference
reaction catal./activity (year)
(␮mol h−1 )

MoS2 /CN-Py flower-like/lamellar in suit solvothermal method 0.05 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA 25 [805] (2016)
␭ > 420 nm
ZnS/g-C3 N4 microsphere/lamellar precipitation method 0.05 4 × UV-LEDs (3 W, Pyrex reactor 25 vol.% CH3 OH 9.7 [806] (2014)
␭ = 420 nm)
WS2 /g-C3 N4 slabs/porous sheet-like gas-solid reaction WS2 /0.01 wt.% 0.05 300 W Xe lamp, Pyrex reactor 25 vol.% CH3 OH WS2 /5.05 [638] (2015)
␭ > 420 nm
WS2 /mpg-C3 N4 mesoporous nanosheets impregnation-sulfidation WS2 /0.3 wt.% 0.05 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA WS2 /6.12 [637] (2014)
method ␭ > 420 nm
CaIn2 S4 /g-C3 N4 nanoplate-lamellar hydrothermal method Pt/1.0 wt.% 0.05 4 × UV-LEDs (3 W, Pyrex reactor 0.5 M Na2 S and Pt/5.1 [807] (2015)
␭ = 420 nm) 0.5 M Na2 SO3
Cu/g-C3 N4 nanoparticles/lamellar H2 reduction Cu 0.05 Xe lamp, ␭ > 400 nm 25 vol.% CH3 OH Cu/1.025 0.35 (420 nm) [674]
(2016)
CuO/g-C3 N4 mono-dispersed wet impregnation-calcination Pt/1.0 wt.% 0.1 300 W Xe lamp, 10 vol.% TEOA Pt/93.7 [808] (2016)
sphere/lamellar method ␭ > 420 nm
Cu(OH)2 /g- clusters/spherical particles precipitation method Cu(OH)2 /0.34mol% 0.1 300 W Xe arc lamp, Pyrex reactor 25 vol.% CH3 OH Cu(OH)2 /4.87 [809] (2014)
C3 N4 ␭ > 400 nm

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

CuO2 /g-C3 N4 nanoparticles/lamellar in situ reduction method Pt/3 wt.% 0.1 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/24.13 [525] (2014)
␭ > 420 nm
CuO2 @g-C3 N4 core@shell octahedra solvothermal and Pt/3 wt.% 0.3 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/79.5 [802] (2015)
chemisorption method ␭ > 420 nm
g-C3 N4 /InVO4 lamellar/nanoparticles hydrothermal method Pt/0.6 wt.% 0.05 300 W Xe arc lamp, 20 vol.% CH3 OH Pt/10.6 4.9 (420 nm) [351] (2015)
␭ > 420 nm
ZnFe2 O4 /g- flakes/lamellar calcinating method Pt/1 wt.% 0.1 300 W Xe arc lamp, Pyrex reactor 10 vol.% TEOA Pt/20 [439] (2014)
C3 N4 ␭ > 430 nm
CuFe2 O4 /g- nanoparticles/lamellar calcinating method Pt/3 wt.% 0.1 300 W Xe lamp, quartz reactor 10 vol.% TEOA Pt/76 [810] (2016)
C3 N4 680 nm >␭ > 420 nm
FeOX /g-C3 N4 granular-like calcinating method Pt/3 wt.%, FeOX (20 g 0.1 300 W Xe lamp, 780 quartz reactor 10 vol.% TEOA FeOX , Pt/108 [811] (2016)
urea/100 mg ferrocene) nm > ␭ > 420 nm
N-CeOx /g-C3 N4 nanoparticles/lamellar one-pot annealing method Pt/1 wt.% 0.05 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/14.62 [812] (2015)
␭ > 420 nm
Ag2 O/g-C3 N4 nanaosheets hydrothermal method 0.01 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA 33.04 [813] (2015)
␭ > 420 nm
Ag2 S/g-C3 N4 particle/mesopores sheets precipitation method 0.05 4 × UV-LEDs (3 W, Pyrex reactor 20 vol.% CH3 OH 10 [665] (2014)
␭ = 420 nm)
TiO2 /g-C3 N4 yolk-shell spheres/lamellar solvothermal method 0.05 4 × UV-LEDs (3 W, Pyrex reactor 25 vol.% CH3 OH 5.6 [814] (2016)
␭ = 420 nm)
g-C3 N4 /B-TiO2 two removed the top of the solvothermal method 0.1 300 W Xe arc lamp, Pyrex reactor 25 vol.% CH3 OH 47.3 [815] (2016)
pyramids ␭ > 400 nm
CoTiO3 /g-C3 N4 rods/lamellar a facial in situ growth method Pt/3 wt.% 0.02 300 W Xe lamp quartz reactor 10 vol.% Pt/11.7 38.4 (365 nm) [816] (2016)
C2 H5 OH
C, nanoparticles/ultrathin one-pot solvothermal method 0.1 300 W Xe lamp, 10 vol.% TEOA 3.92 [817] (2015)
N–TiO2 /g-C3 N4 nanosheets ␭ > 400 nm
N,S–TiO2 /g- semi-spherical in situ thermal induced 0.05 125 W medium 10 vol.% TEOA 317 [818]
C3 N4 nanoparticles/lamellar polymerization method pressure Hg lamp, (2015)
␭ ≥ 400 nm
g-C3 N4 /Pt–TiO2 nanoparticles/nanoparticles/lamellar
chemical 1% wt.%Pt/TiO2 0.1 300 W Xe lamp, Pyrex reactor 10 vol.% TEOA Pt/178 [819] (2012)
adsorption-calcinating method ␭ ≥ 420 nm
g- lamellar/nanosheets/nanorodes
hydrothermal method 0.1 300 W Xe arc lamp, Pyrex reactor 25 vol.% CH3 OH 125 [820]
C3 N4 /MoS2 /TiO2 ␭ > 400 nm (2016)
C3 N4 /rGO/WO3 nanosheets/nanosheets/nanoparticles
hydrothermal method Pt/1 wt.% 0.02 250 W iron doped Pyrex reactor deionized Pt/2.84 0.9 (420 nm) [821] (2015)
metal halid UV–vis water
lamp (␭ > 420 nm)
W18 O49 /g-C3 N4 nanowires/lamellar solvothermal method Pt/3 wt.% 0.005 300 W Xe arc lamp, quartz reactor 10 vol.% TEOA Pt/3.69 1.79 (400 nm) [822] (2016)
␭ > 420 nm

Co-Pi: cobalt-phosphate; MVNTS: multi-walled carbon nanotubes; py:pyridine; CNIC: carbon nitride intercalation compound; C-ZIF: ZIF-8 derived.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 103

lization of low cost Ni(OH)2 as a substitute for noble metals (such

as Pt) in the photocatalytic H2 production for g-C3 N4 . Following
this work, Li and co-workers recently demonstrated that the dual
electron co-catalysts of robust acetylene black and Ni(OH)2 could
significantly enhance the photocatalytic H2 -evolution activity over
g-C3 N4 /Ni (OH)2 hybrid systems. When inserting 0.5% acetylene
black into the interface regions between Ni(OH)2 and g-C3 N4 , a 3.31
time enhancement in H2 -evolution activity can be thus achieved.
It is suggested that the enhanced activity can be attributed to the
effectively promoted separation of photo-generated electron-hole
pairs and enhanced the following H2 -evolution kinetics [155].
Especially, various cheap nanoconbons should be fully integrated
with robust co-catalysts and g-C3 N4 to maximize the functions of
co-catalyst and g-C3 N4 semiconductor.
In addition, several other highly efficient ternary g-C3 N4 -based
photocatalysts have also been developed recently, For instance, Li
Fig. 44. The photocatalytic H2 -evolution rate over g-C3 N4 modified by Pt co- and co-workers confirmed that the CdS photosensitizer and NiS
catalysts with different shapes [823]. co-catalysts in ternary g-C3 N4 -CdS-NiS composites play key roles
in boosting the H2 -generation acticity of g-C3 N4 under visible-
light illumination [197]. The highest H2 -production activity of
solution, whereas the bare g-C3 N4 exhibits the negligible H2 - 2563 ␮molg−1 h−1 is about 1528 times as high as that of the pure
production activity. This is due to the rapid recombination of CB g-C3 N4 (Fig. 46). In another work, when inserting carbon black into
electrons and VB holes, and the large H2 -evolution overpoten- the interfaces between g-C3 N4 and NiS, the average H2 -evolution
tial over pure g-C3 N4 . Subsquently, various engineering strategies, rate of g-C3 N4 /0.5%CB/1.5%NiS can reach 992 ␮mol g−1 h−1 , which
highlighted in the section 4, have been employed to enhance the is about 2.51-fold higher than that of g-C3 N4 /1.5%NiS with a pho-
H2 evolution activity over the g-C3 N4 /Pt systems [369,395,396]. For tocatalytic H2 production rate of 395 ␮mol g−1 h−1 (Fig. 47) [156].
example, Wang and coworkers demonstrated that nanospherical In another paper by Li and co-workers, mpg-C3 N4 /CNT/NiS was
g-C3 N4 frameworks, with interconnecting nanosheets and highly synthesized via the sol-gel method and the direct precipitation pro-
open-up spherical surfaces with sharp edges, achieved an AQY of cess [198]. The results show that the mpg-C3 N4 /CNT/NiS composite
9.6% at 420 nm for H2 evolution [369]. More recently, Cao et al. also exhibits the highest H2 -evolution rate of 521 ␮mol g−1 h−1 , which
demonstrated that the spherical Pt nanoparticles on g-C3 N4 exhib- is about 148 times as high as that of mpg-C3 N4 /CNT. These results
iter much better H2 -evolution activity than those of octahedral highlighted that the ternary hybrid should be a promising direc-
and cubic Pt nanoparticles on g-C3 N4 , due to its favorable exposed tion for constructing highly efficient earth-abundant g-C3 N4 -based
facets, disparity and adsorption energies induced by the spheri- composite H2 -evolution photocatalysts.
cal shape (as shown in Fig. 44) [823]. More interestingly, it was However, there are few attempt reported to reveal the nature
also demonstrated that the single-atom Pt co-catalyst on g-C3 N4 and structural features of the Ni co-catalyst as well as the possi-
exhibited a 8.6-fold enhancement in photocatalytic H2 -evolution ble structural and bonding situation occurring at the co-catalyst
activity, as compared to that of Pt nanoparticles-loaded g-C3 N4 , active sites under light irradiation [676]. To achieve this aim, in situ
due to the maximized atom efficiency and improved surface trap EPR measurements (Fig. 48a) confirmed that a continuous increase
states [664]. Unfortunately, their high cost and low stability signif- of the Ni0 signal was detected (though, not all Ni2+ species were
icantly limit their practical application in a large scale. Therefore, reduced to Ni0 at the same time), indicating the Ni0 acts as the HER
design and preparation of advanced alternative co-catalysts with active sites during the photocatalysis (Fig. 48b) [676]. For other
excellent performance and low cost are of great importance for Ni species, although the electrochemical performances, includ-
the development of these photocatalytic systems. Accordingly, ing polarization curves, time dependence of the current density,
the earth-abundant first-row transition metal electrocatalysts, and electrochemical impedance spectroscopy of g-C3 N4 have been
including Fe-, Co-, Ni- and Cu-based co-catalysts have been of widely determined [197], the accurate catalytic mechanism still
increasing interest in both electrocatalysis and photocatalysis in needs to be uncovered in future. Therefore, both the deep mecha-
the recent years [124,272–274,824]. Importantly, loading suitable nism studies and continuous efforts in developing new co-catalysts
earth-abundant co-catalysts onto the g-C3 N4 provides a facile and are highly expected, to achieve the rational design of highly efficient
strategy to construct real robust g-C3 N4 -based H2 -evolution pho- Ni-based co-catalysts modified g-C3 N4 photocatalysts for practical
tocatalytic systems. Here, we will highlight the unique Ni-based applications.
co-catalysts for enhancing the activity of the g-C3 N4 semiconduc- Finally, it should be pointed out that the oxidation half
tor. reaction of g-C3 N4 should be paid more attention, which is cru-
To date, various kinds of Ni-based co-catalysts, includ- cial for improving the photocatalytic H2 -evolution activity and
ing Ni [192,675,676,825], Ni(OH)x [126,155,669], NiSx deeply understand the underlying mechanism for water splitting
[125,156,197,198,670,672,673], [Ni(TEOA)2 ] Cl2 [679], NiOx [444,685–687]. Clearly, constructing the practical g-C3 N4 -based
[734,792], and Ni(dmgH)2 [677,826] have been widely employed overall water splitting systems is still very challenging. Recently,
as co-catalysts to accelerated the photocatalytic activity of the Kang and coworkers demonstrated that the metal-free carbon
g-C3 N4 for different applications [272]. For example, Yu et al. nanodots–carbon nitride nanocomposite exhibited the impres-
demonstrated that the as-fabricated 0.5 mol% Ni(OH)2 -modified sive performance for photocatalytic solar water splitting [774].
g-C3 N4 composite photocatalysts exhibited the highest H2 - The measured quantum efficiencies of 16% (420), 6.29% (580 nm),
production rate of 7.6 ␮mol h−1 (with an AQE of 1.1% at 420 nm, as and 4.42% (600 nm), correspond to an overall solar energy con-
shown in Fig. 45a), approaching that of optimal 1.0 wt% Pt/g-C3 N4 version efficiency of 2.0%. It was verified that carbon dots-C3 N4
(8.2 ␮mol h−1 ), due to the promoted charge separation and surface catalyzes water splitting to hydrogen and oxygen via the stepwise
reaction rate induced by the loading of Ni(OH)2 (as shown in two-electron/two-electron two-step pathway under visible light
Fig. 45b) [126]. This work perfectly highlighted the promising uti- irradiation. The composite nature of the catalyst provides suffi-
104 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 45. (a) Comparison of the photocatalytic H2 -production activity of the Nix (x, Ni(OH)2 to (g-C3 N4 + Ni(OH)2 ) was 0, 0.1, 0.5, 1.0, 1.6, and 10 (mol%))and Pt-deposited
g-C3 N4 samples in triethanolamine aqueous solution. (b) Charge separation mechanisms in the Ni(OH)2 /g-C3 N4 system under visible light [126].

Fig. 46. (A) Time courses and (B) the average rate of photocatalytic H2 evolution over the photocatalysts: (a) g-C3 N4 ; (b) g-C3 N4 -CdS; (c) g-C3 N4 -9%NiS; (d) CdS-9%NiS; (e)
g-C3 N4 -CdS-3%NiS; (f) g-C3 N4 -CdS-6%NiS; (g) g-C3 N4 -CdS-9%NiS; (h) g-C3 N4 -CdS-12%NiS; (i) g-C3 N4 -CdS-15%NiS [197].

Fig. 47. (A) The average rate of H2 evolution and (B) proposed charge transfer mechanisms in the g-C3 N4 /CB/NiS composite under visible light irradiation: A g-C3 N4 , B
g-C3 N4 -0.5% CB, C g-C3 N4 -1.5% NiS, D g-C3 N4 -0.5%CB-1.5%NiS, E g-C3 N4 -1.0% CB-1.5% NiS, F g-C3 N4 -1.5% CB-1.5% NiS, G g-C3 N4 -1.5% NiS-0.5% CB [156].

Fig. 48. (a) In situ EPR studies of a suspension of Cat-1 in TEOA solution under continuous visible-light irradiation with increasing the time. (b) Charge separation in sg-CN
and the formation of Ni0 nanoparticles during photocatalysis [676].

cient proximity between the H2 O2 generation sites on the C3 N4 and CoOx as redox cocatalysts, can split pure water without the use
surface and the carbon dots so that H2 O2 decomposition and O2 of sacrificial reagents, while pure g-C3 N4 is virtually inactive for
generation in the second stage become efficient [774]. This work overall water splitting by photocatalysis [827]. In addition, the liq-
demonstrated that the control of oxidation half reaction played key uid state Z-scheme systems, including the g-C3 N4 (3 wt% Pt)/WO3
roles in achieving the overall water splitting. More recently, Wang (0.5 wt% Pt)/NaI (5 mM) and g-C3 N4 (3 wt% Pt)/BiVO4 /FeCl2 (2 mM),
and coworkers discovered the irradiated g-C3 N4 loaded by Pt, PtOx , have proven to achieve the overall water splitting [828]. However,
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 105

in these systems, the Pt and PtOx are still the noble metal. Thus, it mentioned two species, the presence of • OH radicals in Ag/g-C3 N4
is clear that developments of low-cost kinetic promoters for both systems further provides the direct evidence for its increased
H2 and O2 evolution are still the major bottleneck for achieving the catalytic performance [489]. The further enhanced photocatalytic
practical H2 evolution or overall water splitting on g-C3 N4 . activity was observed over the Z-scheme Ag@AgBr/g-C3 N4 plas-
monic photocatalyst. It is believed that the Z-scheme system
5.2. Photocatalytic degradation of pollutants retained the photoinduced electrons and hole with strong reduc-
tion and oxidation power in the CB of g-C3 N4 and VB of AgBr,
With rapid growth of population and accelerating industrial- respectively, thus achieving the high efficient photodegradation
ization, the environmental contamination has become a major of MB. During the photocatalysis, the generated Br0 atoms and
threat to public health all over the world. Since the first report superoxide radicals with high oxidizing capabilities are favorable
on heterogeneous photocatalytic remediation of environmental for the further enhancement in the degradation reaction [486].
pollutants (CN− in water) on titania by Frank and Bard in 1977 Furthermore, it is also noted that the g-C3 N4 -based heterojunc-
[829], the heterogeneous photocatalysis has been widely used tions are widely used in the photocatalytic degradation, whereas,
in widespread environmental purification such as air and water few systems were further loaded by co-catalysts. For those systems
purification [309,830–839]. Furthermore, a variety of ways for loaded by co-catalysts, the expensive Ag- and Pt-based co-catalysts
increasing the photodecomposition efficiency of pollutants over are widely chosen. At this point, the atomically dispersed noble-
g-C3 N4 -based semiconductors have been exploited [9,11,20,840], metal co-catalysts with much stronger metal-g-C3 N4 interactions
which have been summarized in Table 8. are considerably promising for the applications of photodegrada-
As observed in Table 8, constructing the g-C3 N4 -based semi- tion [664,694,907]. Therefore, it is expected that more and more
conductor heterojunction and loading suitable O2 -reduction earth-abundant co-catalysts and other modification strategies can
co-catalysts are the general two strategies to achieve the improved be applied in the photocatalyctic degradation of liquid-phase pol-
photocatalytic degradation activity, which will be discussed in this lutants. The homogeneous molecular systems [908] and metal-ion
section. It is clear that the • OH radicals in g-C3 N4 -based photocata- clusters (such as Fe(III) and Cu (II)) [909–916] with the maximum
lysts mainly originated from multi-electron O2 reduction reactions atom utilization efficiency are highly appealing as co-catalysts for
driven by photo-generated electrons on the CB of g-C3 N4 , because applications in the photodegradation of pollutants over g-C3 N4 -
the photo-generated holes exhibited much negative potentials based photocatalysts. What’s more, the deep investigation on the
(1.4 V) than that of • OH/OH− (+2.29 V, vs NHE, pH = 7), leading to the degradation mechanism is also extremely expected. Similar to
failure in driving the oxidation reaction of adsorbed OH− groups to TiO2 -based semiconductors, particular attention should be focused
• OH radicals [83,410]. Thus, for improving the photocatalytic activ- on the investigations on the tunable photocatalytic selectivity of
ity of g-C3 N4 , more efforts have been devoted to strengthening the g-C3 N4 -based photocatalysts towards decomposition of pollutants
decisive O2 -reduction reactions. with positive/negative charge carriers through precisely control-
On the one hand, the photocatalytic degradation of gas-phase ling the surface charge properties of g-C3 N4 [217–219]. In addition,
pollutants over g-C3 N4 -based photocatalysts has been extensively the interesting photocatalytic degradation of antibiotics over g-
investigated, such as NOx [144,883,884], formaldehyde [523], C3 N4 -based multi-junctions and deep mechanisms also deserve
acetaldehyde [539,885] and so forth. For example, Dong and more attention in the near future [481,744,917–919].
coworkers deposited the monodispersed plasmonic Ag nanopar-
ticles onto g-C3 N4 nanosheets to extend visible-light absorption, 5.3. Photocatalytic carbon dioxide reduction
increase the generation of • O2− and enhance the charge separa-
tion, thus achieving the enhanced the photocatalytic activity of From the viewpoint of development of sustainable energy, con-
g-C3 N4 nanosheets towards oxidation of NO to final products [884]. version of the rapidly increasing greenhouse gases to valuable
Katsumata et al. demonstrated that WO3 /g-C3 N4 heterojunction energy-bearing compounds (such as CO, methane, and methanol)
photocatalysts showed a 1.4 times enhancement in photodegrada- using solar energy would be one of the best solutions to overcome
tion of acetaldehyde gas, as compared to pristine g-C3 N4 [539]. In both serious problems of the global warming and shortages of fos-
another paper by Yu et al., a direct TiO2 /g-C3 N4 Z-scheme photocat- sil fuels. Therefore, since the first demonstration of photocatalytic
alyst without an electron mediator (as shown in Fig. 38) exhibited CO2 reduction by Inoue and co-workers in 1979 [920], significant
a high photocatalytic performance in the oxidation decomposition advancements have been made in exploiting efficient and feasi-
of formaldehyde in air [523]. In these studies, the enhancement ble semiconductors for reduction of carbon dioxide with water
in photoactivity was primarily accredited to the improved transfer during last two decades [16,18,921–925]. Among these semicon-
and separation of photogenerated charge carriers and promoted O2 ductor materials, the g-C3 N4 -based photocatalysts have attracted
reduction. A mechanically mixed g-C3 N4 and TiO2 sample with sim- an increasing interesting in selective photocatalytic conversion of
ilar content did not remarkably improve the conversion of NOx , thus CO2 to hydrocarbons or chemicls, due to its excellent stability, suf-
confirming that the interaction between g-C3 N4 and P25 is vital ficiently negative CB levels, innocuity and low price [17,19,658].
for the enhanced activity. EPR measurements once again indicated Significant progresses were summarized in Table 9, which will thor-
that • O2− was the main active species involved in the oxidation oughly discussed in this section.
of NO under both visible and UV light irradiation [886]. In addi- On the one hand, various strategies such as loading co-catalysts
tion, it should be noted that the adsorption of gas-phase pollutants and nanocarbons, doping, constructing Z-scheme and heterojunc-
on the g-C3 N4 should be carefully optimized to achieve the ideal tion, have been widely used to enhance the photocatalytic activity
photocatalytic degradation efficiency. for CO2 reduction [704,940,941]. For example, Yu et al. demon-
On the other hand, the g-C3 N4 -based photocatalysts have strated that the Pt content showed a significant influence on both
been widely used in the photocatalytic degradation of liquid- the activity and selectivity of g-C3 N4 for photocatalytic reduction of
phase pollutants, such as MB [319,506,734,843,887–893], CO2 into CH4 , CH3 OH and HCHO (Fig. 49a) [691]. It is believed that
MO [314,330,576,580,617,688,894–898], RhB the Pt cocatalyst not only facilitates the interfacial electron trans-
[324,330,742,857,858,872,899–906] and so forth. As observed fer from g-C3 N4 to Pt NPs (as shown in Fig. 49b), but also lower
in Table 8, in pure g-C3 N4 -based visible-light systems, the two the overpotential for the CO2 reduction. More recently, Maeda and
main reactive species, • O2− and h+ species, are generally involved his coworkers fabricated the Ru complex decorated g-C3 N4 pho-
in the degradation of pollutants. Interestingly, besides the afore- tocatalysts through the continuous stirring of a methanol solution
 106
Table 8
Summary of the photocatalytic degradation of pollutants over g-C3 N4 -based photocatalysts.

Photocatalyst Structure Synthetic method Co-catal./optimized Mass (g) Light source Targe pollutant/ Degradation Kapp Main active Ref. (year)
mass ratio concentration/volume time/ [10−2 min−1 ] species
efficiency

In2 O3 /g-C3 N4 particles/lamellar calcinating method 0.1 300 W halogen RhB/1 × 10−5 M/100 mL 40 min/99% •
O2 − , • OH [841] (2014)
tungsten lamp,
␭ > ≥ 400 nm
TiO2 –In2 O3 @g- nanoparticles/ solvothermal method 0.08 350 W xenon arc lamp, RhB/0.01 g L−1 /80 mL 60 min/100% 4.6 •
OH [797] (2015)
C3 N4 nanoparticles- lamellar ␭ > 420 nm
CaIn2 S4 /g-C3 N4 nanoplate/lamellar hydrothermal method 0.05 500 W tungsten lamp, MO/0.01 g L−1 /100 mL 120 min/90% •
O2 − , h+ [807] (2015)
␭ > 400 nm
SiO2 /g-C3 N4 core-shell nanosphere calcinating method 0.07 300 W xenon lamp, RhB/0.01 g L−1 /70 mL 150 min/94.3% •
OH, h+ [842] (2015)
␭ ≥ 400 nm
−1 +
g-C3 N4 /TiO2 lamellar/particles sol-gel method 0.1 500 W xenon lamp, MB/0.01 g L /100 mL 360 min/92% h [843] (2016)
␭ > 420 nm
TiO2 /g-C3 N4 core-cell self-assembly method 0.05 500 W xenon lamp, RhB/10 ppm/200 mL 80 min/82% 4.4 [844] (2015)
UV–vis light

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

TiO2 /g-C3 N4 mesoporous melt-infiltrating-calcinating 0.05 500 W xenon lamp, RhB/0.01 g L−1 /50 mL 140 min/100% [845] (2016)
spheres/lamellar method ␭ > 400 nm
−1 • − +
TiO2 /g-C3 N4 yolk-shell spheres/lamellar solvothermal method 0.01 350 W xenon arc lamp, RhB/0.01 g L /80 mL 150 min/99.3% 33.5 O2 , h [814] (2016)
␭ > 420 nm
g-C3 N4 /TiO2 lamellar/nanoparticles calcinating method 0.1 2 × 150 W tungsten ciprofloxacin//0.01 g L−1 / 60 min/95% •
OH, h+ , e− [846] (2015)
lamp, ␭ > 420 nm 100 mL
g-C3 N4 /TiO2 lamellar/roundish particles sol-gel method 0.04 400 W halide lamp, RhB/0.01 g L−1 /40 mL 150 min/100% h+ [436] (2014)
␭ > 400 nm
g-C3 N4 /TiO2 hydrothermal-calcination 0.03 300 W xenon lamp, acyclovir/10 ppm/100 mL 90 min/100% 1.57 h+ [847]
method ␭ > 420 nm (2016)
−1
g-C3 N4 /F-TiO2 lamellar hydrothermal method 0.1 50 W LED light, MB/0.01 g L /100 mL 60 min/89% 3.74 [655] (2014)
␭ = 410 nm
g- lamellar- photodeposition-Physical Ag/2 wt.% 0.03 300 W xenon lamp, MO/0.0135 g L−1 /30 mL 240 min/94% [848] (2014)
C3 N4 /Ag/TiO2 particles/microspheres mixing method ␭ > 420 nm phenol/0.0166 g L−1 /30 mL 240 min/96%
K-Na/g-C3 N4 lamellar calcinating method K-Na co-doped 0.05 250 W high-pressure RhB/1 × 10−5 M/200 mL 120 min/90% 0.86 •
O2 − , • OH [336] (2015)
sodium lamp,
420 < ␭ < 800 nm
mg-C3 N4 mesopores calcinating-dissolving method 0.05 300 W xenon lamp, RhB/0.005 g L−1 /100 mL 20 min/95% [849] (2015)
␭ > 420 nm
g-C3 N4 lamellar thermal condensation 0.02 300 W xenon lamp, 2,4,6-TCP/10−4 M/20 mL 180 min/100% 1.17 •
O2 − , • OOH [850] (2013)
␭ > 420 nm
mg-C3 N4 mesoporous calcinating dissolving method 0.05 300 W xenon lamp, MO/0.01 g L−1 /100 mL 120 min/90% 15.13 [796] (2015)
␭ > 400 nm
−5 •
C60 /mg-C3 N4 particles/lamellar calcinating method C60 /0.03 wt.% 0.025 500 W xenon lamp, MB/1 × 10 M/50 mL 300 min/100% 1.73 OH, h +
[753] (2014)
␭ > 420 nm phenol/5 × 10−6 M/50 mL 300 min/46% 0.15
CDs/g-C3 N4 dots/lamellar mixing-calcinating method carbon dots/0.5 wt.% 0.05 300 W xenon lamp, phenol/0.01 g L−1 /50 mL 200 min/100% [851] (2016)
␭ > 420 nm
C-dots/g-C3 N4 dots/lamellar mixing-calcinating method C-dots/0.25 wt.% 0.1 3 W LED lamp, RhB/1 × 10−5 M/100 mL 60 min/84% 1.3 •
O2 − [745] (2016)
␭ = 365 ± 5 nm
Pd/mpg-C3 N4 particles/mesoporous chemical reduction Pd-doped/1.5 wt.% 350 W xenon lamp, BPA/0.02 g L−1 /50 mL 360 min/100% 1 •
O2 − [729] (2013)
␭ > 420 nm
−1
Pt/C3 N4 nanoparticles/nanotubes hydrothermal method Pt/2 wt.% 0.1 300 W xenon lamp, PCP/0.02 g L /100 mL 420 min/98% [852] (2015)
␭ > 420 nm
Au/Pt/g-C3 N4 particles/lamellar photodeposition method Au/2 wt.%, Pt/0.5 wt.% 0.1 500 W xenon lamp, TC-HCl/0.02 g L−1 /100 mL 180 min/93% 42.86 [481] (2015)
␭ > 400 nm
Au/g-C3 N4 /␣- particles/lamellar/ hydrothermal and Au 0.05 halogen lamp RhB/0.004 g L−1 /250 mL 3.16 [853] (2015)
Fe2 O3 rhombohedral-like ultrasonication method
Table 8 (Continued)

Photocatalyst Structure Synthetic method Co-catal./optimized Mass (g) Light source Targe pollutant/ Degradation Kapp Main active Ref. (year)
mass ratio concentration/volume time/ [10−2 min−1 ] species
efficiency

ZnO@mpg- core-shell physically mixing method 0.025 500 W xenon lamp, MB/1 × 10−5 M/50 mL 150 min/100% 2.05 – [533] (2014)
C3 N4 0.05 ␭ > 420 nm MB/1 × 10−5 M/100 mL – 13.5
500 W xenon lamp,
␭ = 254 nm
ZnO/g-C3 N4 flowerlike/lamellar hydrothermal method 0.02 mild UV light MB/1 × 10−6 M/30 mL 90 min/98.3% [854] (2015)
g- lamellar/particles precipitation and refluxing 0.1 50 W LED lamp RhB/2.5 × 10−5 M/250 mL 270 min/99% 1.54 •
OH [535]
C3 N4 /ZnO/AgCl method (2015)
Zn2 SnO4 /g- particles/lamellar mixing-calcinating method 0.2 300 W xenon lamp, RhB/0.01 g L−1 /100 mL 120 min/97% 3.8 •
O2 − , h+ [855] (2015)
C3 N4 420 < ␭ < 800 nm
V2 O5 /g-C3 N4 particles/lamellar mixing-calcinating method 0.05 250 W xenon lamp, RhB/0.01 g L−1 /100 mL 60 min/95.5% 4.91 ·O2 − , h+ [616] (2016)
␭ > 420 nm
g-C3 N4 /V2 O5 lamellar/nanoparticles one-pot method 0.05 200 W xenon lamp RhB/0.01 g L−1 /50 mL 80 min/100% [856]
(2015)
−1 • − +
GdVO4 /g-C3 N4 small particles/big particles mixing-calcinating method 0.3 350 W xenon lamp, RhB/0.01 g L /300 mL 120 min/96.7% 4.34 O2 , h [857] (2013)
␭ > 420 nm

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

g-C3 N4 /SmVO4 lamellar/aggregated mixing-calcinating method 0.3 350 W xenon lamp, RhB/0.01 g L−1 /300 mL 120 min/100% 3.45 [858] (2013)
particles ␭ > 420 nm
g-C3 N4 /SnO2 lamellar/nanoparticles mixing-calcinating method 0.1 300 W xenon lamp, MO/10 ppm/100 mL 180 min/73% 0.78 [859] (2014)
␭ > 420 nm
−1 • − +
SnNb2 O6 /g- nanosheets/lamellar mixing-calcinating method 0.02 500 W tungsten light MB/0.01 g L /80 mL 240 min/99% 1.73 O2 , h [640] (2016)
C3 N4 lamp, ␭ > 420 nm
Ag/g-C3 N4 particles/lamellar photodeposition method Ag/2 wt.% 0.1 300 W xenon lamp, MO/0.01 g L−1 /100 mL 120 min/100% – [489] (2013)
400 < ␭ < 680 nm PNP/0.01 g L−1 /100 mL 120 min/100% •
O2 − , h+
AgI@ g-C3 N4 core-shell precipitation method 0.1 250 W halide lamp, RhB/0.01 g L−1 /100 mL 120 min/96% 2.52 •
O2 − , h+ , • OH [860] (2015)
␭ > 420 nm
AgCl@pg-C3 N4 nanoparticles/lamellar modified precipitation method 0.2 300 W xenon lamp, atrazine/100 ppm/500 mL 60 min/99% [861] (2015)
␭ > 420 nm
−1 • − + •
Ag3 VO4 /g-C3 N4 particles/lamellar deposition-precipitation 0.05 400 W metal halide RhB/0.005 g L /100 mL 100 min/99.5% 5.56 O2 , h , OH [862] (2015)
method lamp, ␭ > 420 nm
g-C3 N4 /Ag2 O particles/lamellar precipitation method 0.02 300 W xenon lamp, MO/0.02 g L−1 /50 mL 30 min/90% [728] (2013)
␭ ≥ 400 nm phenol/0.02 g L−1 /50 mL 180 min/82%
Ag2 O/g-C3 N4 nanoparticles/lamellar coprecipitation method 0.1 300 W xenon lamp, RhB/0.005 g L−1 /100 mL 40 min/100% 10.53 •
O2 − , h+ [726] (2014)
␭ ≥ 400 nm
−5
Ag@g-C3 N4 core-shell refluxing method Ag/0.5 wt.% 0.025 500 W xenon arc lamp, MB/1 × 10 M/50 mL 1.4 h +
[488] (2014)
␭ > 420 nm
Ag@AgCl/g- nanoparticles/lamellar in situ ion exchange method 0.025 300 W xenon lamp, RhB/0.01 g L−1 /100 mL 30 min/100% 19.54 •
O2 − , h+ [433] (2014)
C3 N4 400 < ␭ < 700 nm
AgVO3 /g-C3 N4 nanoribbons/ultrathin in situ hydrothermal method 0.05 500 W xenon lamp, BF/0.02 g L−1 /50 mL 90 min/100% 5.52 •
OH, h+ [863] (2015)
nanosheets ␭ > 420 nm Bisphenol/0.02 g L−1 /50 mL 90 min/85% 2.08 •
OH, h+
Ag3 PO4 /g-C3 N4 spherical particles/lamellar chemisorptions method 0.02 500 W xenon lamp, MO/0.02 g L−1 /40 mL 60 min/100% 4 h+ [864] (2014)
␭ > 400 nm
−1 • − +
Ag/Fe3 O4 /g- particles/nanoclusters/lamellar
hydrothermal-photodeposition Ag/3 wt.%, Fe3 O4 /9 wt.% 0.05 300 W xenon lamp, tetracycline/0.02 g L /100 mL
90 min/88% 2.18 O2 , h [865] (2016)
C3 N4 method ␭ > 420 nm
g-C3 N4 /CdS lamellar/nanotube precipitation method 0.08 500 W xenon lamp, MB/0.025 g L−1 /200 mL 180 min/90.45% •
OH, h+ [506] (2014)
␭ > 420 nm
CdS QDs/lamellar mixing-calcinating method 0.1 500 W tungsten light RhB/0.01 g L−1 /100 mL 90 min/88.2% •
O2 − , h+ [866] (2016)
QDs/npg-C3 N4 lamp, ␭ > 400 nm
−5 •
CdWO4 /g-C3 N4 nanorods/lamellar mixing-calcinating method 0.05 500 W xenon lamp, RhB/1 × 10 M/50 mL 240 min/46% 0.27 OH, h +
[867] (2015)
␭ ≥ 400 nm
Cd0.2 Zn0.8 S/g- nanoparticles/lamellar hydrothermal method 0.05 500 W xenon lamp, RhB/0.01 g L−1 /50 mL 80 min/95.8% [802] (2015)
C3 N4 ␭ > 420 nm phenol/0.01 g L−1 /50 mL 180 min/76.1%
BiPO4 /mg-C3 N4 nanorods/mesoporous in situ method 0.1 300 W xenon arc lamp, MO/0.02 g L−1 /100 mL 120 min/100% 0.77 [868] (2014)
␭ > 420 nm

107
 108
Table 8 (Continued)

Photocatalyst Structure Synthetic method Co-catal./optimized Mass (g) Light source Targe pollutant/ Degradation Kapp Main active Ref. (year)
mass ratio concentration/volume time/ [10−2 min−1 ] species
efficiency

BiOCl/C3 N4 flowerlike/amorphous solvothermal method 0.2 300 W xenon arc lamp, MO/0.01 g L−1 /500 mL 80 min/95% h+ [869] (2013)
␭ > 400 nm
−1 +
g-C3 N4 /BiOBr lamellar/nanosheets deposition-precipitation 0.02 400 W halogen lamp, RhB/0.06 g L /40 mL 100 min/98% 4.01 h [870] (2013)
method 0.04 ␭ > 400 nm 2,4-DCP/0.01 g L−1 /40 mL 180 min/80% 3.91 •
OH
•
BiOx Iy /g-C3 N4 square thin-plates/lamellar controlled hydrothermal 0.01 100 W xenon arc lamp CV/10 ppm/100 mL 36 h/99% 0.283 O2 − [871]
(2016)
g- lamellar/plates mixing-calcinating method 0.05 1000 W xenon lamp, RhB/1 × 10−5 M/50 mL 240 min/56% 17 •
O2 − , h+ [872] (2014)
C3 N4 /Bi2 O2 CO3 ␭ > 420 nm
g- lamellar/nanosheets hydrothermal method 0.4 300 W xenon lamp, MO/0.01 g L−1 /200 mL 180 min/94.82%1.66 [580] (2014)
C3 N4 /Bi2 WO6 ␭ > 400 nm
Bi2 WO6 QDS-lamellar in situ method 0.05 300 W xenon lamp, RhB/0.01 g L−1 /50 mL 30 min/100% 16.8 •
O2 − , h+ , • OH [505] (2015)
␭ ≥ 400 nm

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

QDS/g-C3 N4
g- agglomeration mixing-calcinating method 0.15 500 W xenon lamp, MO/0.01 g L−1 /50 mL 180 min/99.9% 3.66 [576] (2011)
C3 N4 /Bi2 WO6 ␭ > 420 nm
g- lamellar-hollow sphere hydrothermal method 0.02 400 W metal halide RhB/0.01 g L−1 /50 mL 70 min/98% 5.15 •
O2 − [873] (2014)
C3 N4 /Bi2 MoO6 lamp, ␭ ≥ 420 nm
−1 • −
g- lamellar-flakelike hydrothermal method 0.1 400 W xenon lamp, MO/0.005 g L /100 mL 120 min/93% – O2 [874] (2013)
C3 N4 /Bi2 WO6 ␭ > 400 nm 2,4-DCP/0.02 g L−1 /100 mL 300 min/92% 0.856
g- lamellar/particles ball milling 2 g L−1 500 W xenon lamp, acid orange II/0.05 g L−1 4.1 •
O2 − , h+ [875]
C3 N4 /Bi4 Ti3 O12 ␭ > 420 nm (2016)
HSbO3 /g-C3 N4 small particles/big particles mixing-calcinating method 0.3 400 W RhB/0.015 g L−1 /100 mL 240 min/90% 1.41 •
O2 − [876] (2015)
halogen-tungsten
lamp, ␭ > 420 nm
•
CuTCPP/g-C3 N4 rodlike/lamellar ethanol dispersion method 0.025 500 W xenon lamp, phenol/5 ppm/50 mL 0.04 O2 − , h+ [877] (2015)
␭ > 420 nm
g-C3 N4 /CuOx lamellar/nanoparticles mixed solvent-thermal method 0.01 350 W xenon lamp MO/0.02 g L−1 /50 mL 70 min/83.3% 2.05 •
O2 − , h+ [878] (2016)
␤-Fe2 O3 /g- nanoparticles in situ growth strategy method 0.2 300 W xenon arc lamp, MO/0.01 g L−1 /160 mL 240 min/86% 0.88 •
O2 − , • OH [587] (2016)
C3 N4 ␭ > 420 nm
•
[WO4 ]2− /g- lamellar calcinating method [WO4 ]2— doped 0.1 300 W xenon lamp, RhB/10 ppm/100 mL 90 min/87% 2.2 O2 − , • OH [879] (2015)
C3 N4 ␭ > 420 nm
−1
WO3 /g-C3 N4 nanorods/lamellar mixing-calcinating method 0.05 500 W tungsten lamp RhB/0.005 g L /100 mL 90 min/91% 2.61 [544] (2015)
H3 PW12 O40 /C3 Nparticles/tubular
4 hydrothermal method 0.2 300 W xenon lamp, MO/0.01 g L−1 /100 mL 240 min/99% [880] (2014)
NTs ␭ > 420 nm DEP/0.01 g L−1 /100 mL 1440 min/85%
g-C3 N4 /MoO3 lamellar/broader particles mixing-calcinating method 0.1 300 W xenon lamp, MB/0.01 g L−1 /100 mL 180 min/93% 1.47 [881] (2013)
␭ > 400 nm
g- lamellar/nanoparticles solvothermal method 0.03 50 W LED light, MB/0.01 g L−1 /30 mL 40 min/90% 6.88 [604]
C3 N4 /Bi2 MoO6 ␭ = 410 nm (2015)
−1 +
MoS2 /g-C3 N4 nanosheets/lamellar impregnation and calcinating 0.04 300 W xenon lamp, RhB/0.01 g L /50 mL 20 min/96% 15.2 h [633] (2016)
method ␭ > 400 nm MO/0.01 g L−1 /50 mL 180 min/95% 1.61 h+
•
Ce/g-C3 N4 lamellar calcinating method Ce-doped 0.05 250 W high-pressure RhB/10 ppm/200 mL 120 min/90% 1.55 O2 − [882] (2015)
sodium lamp,
400 < ␭ < 800 nm
CoO4 /g-C3 N4 lamellar mixing and heating method CoO4 -doped/0.2 wt.% 0.1 250 W xenon lamp, MO/0.01 g L−1 /100 mL 120 min/100% •
O2 − [688] (2014)
␭ > 420 nm
−1
NiO/g-C3 N4 nanoparticles/lamellar calcinating method 0.05 500 W xenon lamp, MB/0.005 g L /100 mL 40 min/100% 5.1 [734] (2014)
␭ > 420 nm
Table 9
Summary of the photocatalytic CO2 reduction over g-C3 N4 -based photocatalysts.

Material Morphologies and Synthesis method Cocatalyst Light source Mass [g]/systems/Volume Selective products Ref. (year)
microstructures [mL] (activity) [␮M h−1 g−1 ]

Gas-solid systems for CO2 photoreduction

Ag3 PO4 /g-C3 N4 nanoparticles/nanosheets direct thermolysis 300 W Xe lamp, / CO(44) CH3 OH(8.5) [608] (2015)
in-situ deposition ␭ ≥ 420 nm CH4 (2) C2 H5 OH(1.1)
g-C3 N4 /Bi2 WO6 Bi2 WO6 nanoflakes/thin layer in situ hydrothermal approach 300 W Xe lamp, 0.1/CO2 and CO(5.19) [926] (2015)
g-C3 N4 nanosheets ␭ ≥ 420 nm H2 O vapor/500 mL
m-CeO2 /g-C3 N4 mesoporous hard-template route 300 W of Xenon-arc 0.05/CO2 and CO(10.16) CH4 (13.88) [927] (2016)
lamp H2 O vapor/500 mL
g-C3 N4 /KNbO3 g-C3 N4 nanosheets/layered ultrasonic dispersion followed 300 W Xe lamp, 0.1/CO2 and H2 O vapor CH4 (2.5) [693] (2015)
structure KNbO3 by heat treatment method ␭≥ 420 nm
SnO2-x /g-C3 N4 SnO2-x nanoparticles/g-C3N4 directly calcining 500 W Xe lamp 0.02/CO2 and H2 O vapor CO(19.2) CH4(1.4) [928] (2015)
sheets are simple calcination of g-C3 N4 CH3 OH(3.1)
and Sn6 O4 (OH) 4
g-C3 N4 /NaNbO3 NaNbO3 nanowires/g-C3 N4 calcination 300 W xenon arc lamp 0.05/CO2 and H2 O CH4 (6.4) [929] (2014)
nanosheets ␭ > 420 nm vapor/230 mL
g-C3 N4 -N-TiO2 TiO2 nanoparticles/g-C3 N4 in situ synthesized by thermal / 300 W xenon arc lamp 0.1/CO2 and H2 O CO(12.25) [930] (2014)

J. Wen et al. / Applied Surface Science 391 (2017) 72–123

nanosheets treatment vapor/780 mL
Mo-doped g-C3 N4 worm-like mesostructures simple pyrolysis method / 300 W Hg lamp 0.1/CO2 and H2 O CO(111) CH4 (15.4) [931] (2016)
vapor/2700 mL
C3 N4 –MCF sponge-like structure hard-template synthesis / / / CH3 CHO(8) [932] (2015)
B4 C/C3 N4 B4 C particles/g-C3 N4 solvent evaporation 0.8%wt Pt 300 W Xenon short arc 0.006/CO2 and H2 O CH4 (0.85) [933] (2016)
nanosheets method lamp vapor/100 mL
405 nm < ␭ < 723 nm
Pt/g-C3 N4 nanoparticles/lamellar chemical reduction process in 2 wt% Pt 15 W energy-saving CO2 and H2 O vapor CH4 (1.302) [692] (2015)
ethylene glycol daylight bulb
S-doped g-C3 N4 layered structures contain simply calcinating thiourea 1 wt% Pt 300-W simulated solar 0.1 g/CO2 and H2 O CH3 CHO(0.37) [199] (2015)
many irregular pore sizes Xe arc lamp vapor/200 mL
ZnO/g-C3 N4 highly mesoporous a simple impregnation method 500 W Xe lamp 0.01/CO2 and H2 O CO(39) CH3OH(10) [536] (2015)
vapor/132 mL CH4(4) C2H5OH(1.5)
g-C3 N4 /ZnO ZnO microcrystals/g-C3 N4 a one-step facile calcination 300 W simulated solar 0.1/CO2 and H2 O CH3 OH(0.6) [220] (2015)
nanosheets method Xe arc lamp vapor/200 mL
RGO/g-C3 N4 sandwich-Like Hybrid electrostatic self-assembly 15 wt% RGO 15 W energy-saving CO2 and H2 O vapor CH4 (1.393) [934] (2015)
Nanosheets construction of 2D/2D Daylight bulb
BiOI/g-C3 N4 BiOI particles/g-C3N4 in situ syntheized 300 W xenon arc lamp 0.1/CO2 and H2 O CO(3.44) CH4 (0.2) [614] (2016)
nanosheets (␭ > 400 nm). vapor/180 mL
g-C3 N4 –Pt two-dimensional lamellar directly heating and Pt was 1 wt% Pt 300 W simulated solar 0.1/CO2 and H2 O CH4(0.3) HCHO(0.075) [691] (2014)
structure and numerous deposited on g-C3 N4 Xe arc lamp vapor/200 mL CH3OH(0.24)
randomly organized
nanosheets
AgX/g-C3 N4 (X = Cl and irregular spheres of sonication-assisted 500 W Xenon arc lamp, 0.1/CO2 and H2 O vapor 30%AgBr/g-C3 N4 [935] (2016)
Br) AgX/g-C3N4 nanosheets deposition-precipitation (␭ > 400 nm) CH4 (1.092)
approach
AgCl/C3 N4 AgCl nanoparticles/C3 N4 in situ 15 W energy-saving CO2 and H2 O vapor CH4 (0.95) [936] (2016)
nanosheet deposition–precipitation daylight lamp
approach.
GO-g-C3 N4 sandwich-like a facile one-pot 15 wt% GO 15 W energy-saving CO2 and H2 O vapor CH4 (5.87) [702] (2015)
impregnation–thermal daylight bulb
reduction strategy
RGO/p-C3 N4 sandwich-like a novel combined ultrasonic 15 wt% rGO 15 W energy-saving 0.1 g/CO2 and H2 O vapor CH4 (1.393) [160] (2015)
dispersion and electrostatic daylight lamp
self-assembly strategy
g-C3 N4 /ZnO a direct Z-scheme mechanism a one-step facile calcination 300 W simulated solar 0.1 g/CO2 and H2 O CH3 OH(0.6) [601] (2015)
method Xe arc lamp vapor/200 mL

109
110 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

containing two materials at room temperature overnight [695]. The

[697] (2016)

[937] (2015)

[227] (2015)

[938] (2015)

[939] (2016)
[708] (2015)

[620] (2014)
resulting heterogeneous photocatalyst systems could achieve the
Ref. (year)

highest apparent quantum yield of 5.7% at 400 nm for the pho-

tocatalytic reduction of CO2 into formic acid under visible-light
irradiation (as shown in Fig. 50) [695]. Surprisingly, the ternary
hybrid of plasmonic Ag nanoparticles and g-C3 N4 /binuclear Ru(II)
(activity) [␮M h−1 g−1 ]

complex could achieve a very high turnover number of > 33,000

with a high selectivity of 87–99% for HCOOH production, due to the
Selective products

Ag/g-C3 N4 + WO3 :

HCOOH (1352.07)
Au/g-C3 N4 + WO3
combination effects of plasmonic Ag and Z-Scheme charge trans-

CH3 OH(24.05)

CH3 OH(34.02)
CH3 OH(0.28)
HCOOH(7.8)

fer (as shown in Fig. 51) [700]. These are the best values that have
CH4 (0.75)

CH4 (0.34)

CO(469)
been reported for heterogeneous photocatalysts for CO2 reduction
CO(9.9)

under visible-light irradiation to date. The present study clearly

highlighted the great potential of complex molecular co-catalyst
on carbon nitride in photocatalytic CO2 reduction under visible
0.005/CO2 and MeCN/TEOA

80 mL CO2 saturated water

light. Thus, it is expected that the multi coupling of complex molec-

Mass [g]/systems/Volume

methanol solution/20 mL
0.1/CO2 saturated water

ular co-catalyst, g-C3 N4 and other photosensitizers may provide

mixture (4:1, v/v) 4 mL

solution (MeCN/TEOA
5 mL CO2 saturated of

exciting opportunities for promising CO2 photoreduction over g-

0.003/CO2 and H2 O

0.03/CO2 saturated

0.02/CO2 saturated
solution of CoCl2 ,

triethanolamine
C3 N4 -based photocatalysts. In addition, it is also noted from Table 9
solution/200 mL

2,2-bipyridine,
that there are few earth-abundant co-catalysts reported to accel-
4:1)/330 mL

erate the CO2 photoreduction over g-C3 N4 -based photocatalysts,

solution

which should be urgently developed in the near future. At this

[mL]

point, the nano-carbons, such as RGO and CNTs, are highly expected
to coupling with the g-C3 N4 to obtain highly efficient metal-free
g-C3 N4 -based photocatalysts for CO2 photoreduction [934].
pressure Hg lamp with
a NaNO2 solution filter

300 W xenon arclamp,

Besides co-catalysts, doping and nanostructured heterojunction

light-emitting diode
400 nm< ␭ < 800 nm

300 W Xe arc lamp

(LED), ␭ = 435 nm

were also extensively used to enhance the visible light absorp-

300 W Xe lamp,

300 W Xe lamp,

tion and photocatalytic CO2 reduction activity of g-C3 N4 -based

250 W lamp,
Light source

400 W high

␭ = 365 nm
␭ > 420 nm

␭ > 420 nm

photocatalysts. Wang et al. fabricated sulfur-doped g-C3 N4 pho-

tocatalysts by employing thiourea as the sulfur precursor for the
reduction of CO2 to CH3 OH [199]. The DFT studies confirmed that
the electrons can be easily excited from the VB to the impurity
state, and then to the CB of sulfur-doped g-C3 N4 owing to the
impurity sulfur doping (as shown in Fig. 52a), which induced addi-
0.5%wt Au,
Cocatalyst

0.5%wt Ag

tional electrons, resulting in the spin polarization. As the band

gap was narrowed from 2.7 to 2.63 eV, the light absorption was
RuP

broadened in the sulfur-doped g-C3 N4 , generating more elec-

/

trons and holes under the light irradiation. Thus, the CH3 OH yield
(1.12 ␮mol g−1 ) was 1.5 times higher than that the unmodified g-
C3 N4 (0.81 ␮mol g−1 ) (as shown in Fig. 52b). In another example,
simple thermal condensation

Yu et al. constructed a binary g-C3 N4 /ZnO photocatalyst with an

a facile one-pot chemical
photodeposition method
amine functionalization

hydrothermal methods
polycondensation and
self-assembly method
thermal condensation

intimate contact interface via a one-step facile calcination method

condensation of urea

[220]. The results showed that the as-prepared g-C3 N4 /ZnO pho-
facile electrostatic
Synthesis method

tocatalytic system exhibited enhanced photocatalytic activity for

planetary mill
of melamine

CO 2 reduction by a factor of 2.3 compared with pure g-C3 N4 (as

adsorption

shown in Fig. 53a). The better performances of the g-C3 N4 /ZnO

binary composite photocatalytic system could be well explained
by the direct Z-scheme mechanism rather than the conventional
heterojunction-type mechanism (as shown in Fig. 53b and c), which
nanospheres/flaky morphology

was achieved due to the highly efficient ZnO-to-g-C3 N4 electron

two-dimensional lamellar and
ten layers CNNS/the UiO-66

dense and stacked particles

transfer occurring at the intimate contact interface between the g-

particles/g-C3 N4 particles

C3 N4 phase and ZnO phase. This work highlighted that the rational
mesoporous structure

porous structure with

highly dispersed WO3

construction of direct Z-scheme g-C3 N4 -based photocatalytic sys-

Morphologies and

anomalous shape

tem without an electron mediator should be promising strategy for

thin nanosheets
microstructures

Suspension systems for CO2 photoreduction

microspheres

the applications in the photocatalytic CO2 reduction.

and sheets

On the other hand, the product selectivity of photocatalytic CO2

reduction should be also a major consideration in designing semi-
conductor photocatalysts [942]. For example, Liu and coworkers
obtained the g-C3 N4 nanosheets by the thermal delamination of
bulk g-C3 N4 in air. It was shown that g-C3 N4 nanosheets with a band
2D hydroxyl-rich C3 N4

amine-functionalized

gap of 2.97 eV yielded the major product of CH4 , whereas bulk g-

UiO-66/10%CNNS

C3 N4 with a smaller band gap of 2.77 eV formed the main product of

Table 9 (Continued)

g-C3 N4 (P-CW)

CH3 CHO (Fig. 54a) [409]. This elucidated that the nanosheets had a
RuP/g-C3 N4

CdS/g-C3 N4
nanosheets

larger band gap by 0.2 eV, leading to a lower VB edge by 80 meV and
CNU–BAX
Material

a higher CB edge by 120 meV. Therefore, the nanosheets provided a

g-C3 N4

WO3 /

larger thermodynamic diving force for the hole and electron trans-
fer by means of a greater difference in energy level between redox
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 111

Fig. 49. (a) Photoconversion of CO2 into CH4 , CH3 OH and HCHO over PtX -loaded g-C3 N4 (x, the weight percentage ratios of Pt against g-C3 N4 were 0, 0.25, 0.5, 0.75, 1.0 and
2.0 wt%); (b) Charge separation mechanisms in the Pt/g-C3 N4 systems [691].

to confirm the obtained prodcuts stemmed from the photofixation

of CO2 in order to exclude the possibility of photodissociation of
the organic impurities or even carbon-containing catalysts.

5.4. Photocatalytic selective organic transformations

Recently, the robust metal-free g-C3 N4 -based photocatalysts

have been shown to have great potential for selective organic
transformation under mild conditions, including oxidation of aro-
matic compounds [395,507,946–956], photo catalytic esterification
Fig. 50. Scheme illustration for CO2 reduction using a Ru complex/C3 N4 hybrid
photocatalyst.
of benzaldehyde and alcohol [957], oxidative cleavage of the
carbon–carbon bond of ␣-hydroxy ketones [958] and allylic oxi-
dation [959]. For example, Wang and coworkers demonstrated
that direct oxidation of benzene to phenol with H2 O2 catalyzed
by porous Fe-g-C3 N4 could be achieved, in both the presence and
absence of visible light irradiation [950]. By taking advantage of
the photocatalytic functions of g-C3 N4 , the yield of the phenol syn-
thesis can be markedly improved. Furthermore, the same research
group demonstrated that the metal-free graphene sheet/g-C3 N4
nanocomposite could achieve the selective photocatalytic oxida-
tion of cyclohexane to cyclohexanone through the superoxide
radical anion (• O2 − ) induced from the activation of O2 (as shown
in Fig. 55), highlighting the key roles of O2 -reduction reaction
in the photocatalytic selective organic transformations [244]. In
another report, Zhang et al. [956] revealed that a 38% conversion
of benzene to phenol with 97% selectivity could be achieved using
FeCl3 -modified mesoporous carbon nitride as a visible-light photo-
catalyst to activate H2 O2 . Li et al. [960] developed a Mott–Schottky
Fig. 51. Scheme illustration for Z-Scheme CO2 reduction using a ternary Hybrid of photocatalyst consisting of mesoporous carbon nitride with Pd
Ag/g-C3 N4 /Binuclear Ru(II) Complex [700]. nanoparticles. The efficient electron transfer from the g-C3 N4 to the
Pd resulted in a high photocatalytic activity and selectivity for the
potentials of the reactants and band edges (Fig. 54b). This indi- room-temperature C C bond formation by coupling aryl halides
rectly led to a larger proportion of long-lived charge carriers for the with different coupling partners. More recently, Yin and coworkers
nanosheets in contrast to the bulk. As a consequence, the formation demonstrated that an acid-base bifunctional P-doped g-C3 N4 pho-
of CH4 was more favorable due to rapid transfer of photoexcited tocatalysts could achieve the cycloaddition reactions, due to the
electrons in the nanosheets to the intermediate species. synergetic effect of acid (halide anions) and basic sites for ring open-
However, it is worth mentioning that the current apparent ing of epoxide and adsorption/activation of CO2 [325]. In future, it
quantum efficiency is still low for the commercial applications. is expected that various kinds of multifunctional g-C3 N4 composite
Thus, there is still ample room to further improve the CO2 pho- photocatalysts could be widely used in the selective photocatalytic
toreduction in g-C3 N4 -based photocatalytic system. Furthermore, organic transformations, which are hardly proceed by traditionary
the exact reaction mechanism for the CO2 photoreduction should thermal catalysis. Also, the deep mechanism investigation is highly
be paid more attention. In this regard, various strategies to enhance desired.
the CO2 adsorption of porous absorbents could be employed to
improve the adsorption and activation of CO2 on g-C3 N4 -based 5.5. Photocatalytic disinfection
photocatalysts [943–945]. Especially, the selectivity of CO2 pho-
toreduction should be deeply investigated for each system. In fact, As a nontoxic, efficient, and stable method, photocatalytic
it is strongly suggested that all products from the CO2 conversion disinfection has been shown to be superior in comparison with tra-
requires should be measured, in gas and liquid phase for suspension ditional water disinfection methods, including chlorination, ozone,
systems. To well understand the photocatalytic reaction steps, DFT and ultraviolet (UV), have some disadvantages [659]. Commonly,
can be used to identify the activation state of CO2 . In addition, the the toxic metals in the efficient metal-based photocatalysts for
isotopic labeling analysis using 13CO2 as the reactant is nacessary bacterial inactivation is unfavorable for “green” water disinfection
112 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Fig. 52. (a) Schematic of band structure of pure g-C3 N4 (left) and S-doped g-C3 N4 (right); (b) Comparison of photocatalytic CH3 OH production over S-doped g-C3 N4 (TCN)
and un-doped g-C3 N4 (MCN) at 3 h under UV–vis light irradiation [199].

Fig. 53. Comparison of photocatalytic CH3 OH production rates of cm-ZnO, pure ZnO, G10, and pure g-C3 N4 . Schematic illustration of two different mechanisms for charge
carrier separation: (b) conventional heterojunction-type and (c) direct Z-scheme mechanisms [220].

Fig. 54. (a) Schematic illustration of the photoreduction CO2 to CH3 CHO and CH4 on bulk g-C3 N4 and g-C3 N4 nanosheets. (b) Band structures of g-C3 N4 nanosheets (left) and
bulk g-C3 N4 (right) and the redox potentials of the reactions [409].

alytic inactivation of bacteria over g-C3 N4 [450,659,660,961]. For

example, Huang et al. demonstrated that metal-free robust g-C3 N4
photocatalyst exhibit antibacterial activity for the inactivation of
Escherichia coli K-12 (E. coli) under visible light irradiation [961].
Especially, a novel heterojunction related to g-C3 N4 was synthe-
sized via cowrapping the RGO and g-C3 N4 (CN) sheets on ␣-sulfur
(␣-S8 ) by Wang and his coworkers. The results indicated that
the visible-light-driven photocatalytic activities of this system for
bacterial inactivation was significantly improved, which will also
change with the shells arrangement evolution of RGO and CN.
The enhanced activities can be ascribed to the electrons or holes
migration in the system as shown in Fig. 56 [660]. In addition,
Zhao et al. indicated that the atomic single layer g-C3 N4 with the
thickness of 0.5 nm exhibited performance of photocatalytic disin-
Fig. 55. Schematic illustration of the selective oxidation of secondary C H bonds fection for inactivation of Escherichia coli, due to low charge transfer
of cyclohexane through the superoxide radical anion (• O2 − ) [244]. resistance and efficient charge separation [450]. More recently, An
and coworkers demonstrated that the g-C3 N4 /TiO2 hybrid photo-
catalyst, comprised of micron-sized TiO2 spheres wrapped with
[660]. At this point, the robust and non-toxic metal-free g-C3 N4
lamellar g-C3 N4 , exhibited significantly enhanced photocatalytic
seems to be more promising in water disinfection. However, limited
studies have concentrated on the visible-light-induced photocat-
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 113

Fig. 56. Schematic illustration of the visible-light-driven photocatalytic bacterial inactivation mechanisms of (a) CNRGOS8 ; (b) RGOCNS8 in aerobic condition; (c) CNRGOS8 ;
(d) RGOCNS8 in anaerobic condition [660].

activity for the inactivation of Escherichia coli K-12, due to improved and nanocarbon loading seem to be more promising in developing
light absorption and the effective charge separation [659]. practical g-C3 N4 -based photocatalysts. Typically, Z-scheme con-
struction is more interesting and promising than the traditional
heterojunction. At this point, more investigations should be paid
6. Conclusions and future prospects
to this strategy. Absolutely, the developments of earth-abundant
co-catalysts are still a hard task in these photocatalytic fields. The
In summary, this review highlights the advantages, versatile
magical nanocarbons will play the irreplaceable roles in construct-
properties, design strategies and potential application of robust
ing highly efficient g-C3 N4 -based photocatalysts for all the time.
g-C3 N4 -based composite photocatalysts. Obviously, g-C3 N4 has
In addition, the applications of g-C3 N4 -based photocatalysts are
proven to be one of the most promising candidates suitable
mainly focused on the H2 evolution and degradation of pollutants.
for designing and fabricating advanced composite photocatalysts
However, the photocatalytic CO2 reduction over g-C3 N4 -based
for various applications. Therefore, there is little doubt that the
photocatalysts become more and more attractive in the past three
explosive growth of g-C3 N4 -based composite photocatalysts will
years. The basic nature of the g-C3 N4 surface determines its bright
continue to accelerate in the near future. To date, although con-
future in the fields of CO2 reduction. Furthermore, work on the
siderable progress has been achieved in the recent years, there
O2 evolution from the other half-reaction of H2 O splitting should
are still many challenges to rationally fabricate the highly effi-
gain more attention in the near future, which involves in both
cient g-C3 N4 -based photocatalysts towards various applications
the water splitting and CO2 reduction. Additionally, the exact
and deeply understand the underlying enhancement mechanism
reaction mechanism, particularly the CO2 reduction using g-C3 N4 -
of composite photocatalysts by g-C3 N4 . There are still many open
based photocatalysts, still remains doubtful and unresolved to date.
issues and opportunities for further research effort. Accordingly,
The deep studying of reaction pathways is crucial for revealing
more studies are also needed to make full use of the outstand-
the photocatalytic enhancement fundamental and further ratio-
ing structural and electronic properties of g-C3 N4 in the composite
nally design the highly efficient g-C3 N4 -based photocatalysts in
photocatalysts.
the future. Furthermore, some key issues that account for the
On the one hand, versatile properties of g-C3 N4 -based photo-
high photocatalytic activity, i.e. optical absorption, electronic band
catalysts are still needed to be explored carefully. Since the highly
structure, and charge transfer dynamics, should be exhaustively
effective and stable g-C3 N4 -based photocatalysts with narrowed
investigated to gain theoretical insights by means of both computa-
band gaps are difficult to obtain, the design and development of
tional (first-principles DFT) and experimental simulations. In terms
conjugated narrow-band polymer might provide alternative ideas
of experimental work, reactant adsorption sites, charge transfer
for boosting the advancements of photocatalysis based on the
dynamics, and molecular orbitals should also be deeply researched.
organic semiconductors [962–968]. Furthermore, the accurate con-
The joint efforts by researchers from various fields and countries
trol of surface defects and facile scale preparation methods of
must bring one and one exciting time for g-C3 N4 -based photocat-
g-C3 N4 nanosheets are highly desired. The advanced electrocata-
alysts.
lysts and photoelectrocatalysts based g-C3 N4 should be exploited
as an important research community for extending the applications
of g-C3 N4 -based photocatalysts. Among various design strategies,
the dimensionality tuning, pore texture tailoring, heterojunction
construction (especially for Z-scheme construction), co-catalyst
114 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

Acknowledgments [54] Y. Zheng, L. Lin, B. Wang, X. Wang, Angew. Chem. Int. Ed. 54 (2015)
12868–12884.
[55] J. Liu, H. Wang, M. Antonietti, Chem. Soc. Rev. 45 (2016) 2308–2326.
Li would like to thank Industry and Research Collaborative [56] X. Dong, F. Cheng, J. Mater. Chem. A 3 (2015) 23642–23652.
Innovation Major Projects of Guangzhou (201508020098), NSFC [57] Y. Gong, M. Li, H. Li, Y. Wang, Green Chem. 17 (2015) 715–736.
(20906034) and the State Key Laboratory of Advanced Technology [58] N. Zhang, M.-Q. Yang, S. Liu, Y. Sun, Y.-J. Xu, Chem. Rev. 115 (2015)
10307–10377.
for Material Synthesis and Processing (Wuhan University of Tech- [59] W.-J. Ong, L.-L. Tan, Y.H. Ng, S.-T. Yong, S.-P. Chai, Chem. Rev. 116 (2016)
nology) (2015-KF-7) for their support. X. Chen would like to thank 7159–7329.
the College of Arts and Sciences, University of Missouri—Kansas [60] X. Chen, Q. Liu, Q. Wu, P. Du, J. Zhu, S. Dai, S. Yang, Adv. Funct. Mater. 26
(2016) 1719–1728.
City and University of Missouri Research Board for their financial
[61] L. Zhou, Y. Xu, W. Yu, X. Guo, S. Yu, J. Zhang, C. Li, J. Mater. Chem. A 4 (2016)
support. 8000–8004.
[62] I. Yuta, K. Toshiaki, T. Hidekazu, S. Masaya, K. Shinsuke, T. Kenichi, I. Kunio,
Jpn. J. Appl. Phys. 47 (2008) 7842.
[63] R. Reyes, C. Legnani, P.M. Ribeiro Pinto, M. Cremona, P.J.G. de Araújo, C.A.
References Achete, Appl. Phys. Lett. 82 (2003) 4017–4019.
[64] J. Liang, Y. Zheng, J. Chen, J. Liu, D. Hulicova-Jurcakova, M. Jaroniec, S.Z. Qiao,
[1] A. Fujishima, K. Honda, Nature 238 (1972) 37–38. Angew. Chem. Int. Ed. 51 (2012) 3892–3896.
[2] B. Kraeutler, A.J. Bard, J. Am. Chem. Soc. 100 (1978) 4317–4318. [65] T.Y. Ma, S. Dai, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. Ed. 53 (2014)
[3] A.J. Bard, J. Photochem. 10 (1979) 59–75. 7281–7285.
[4] A.J. Bard, Science 207 (1980) 139–144. [66] S. Yang, X. Feng, X. Wang, K. Muellen, Angew. Chem. Int. Ed. 50 (2011)
[5] A.J. Bard, J. Phys. Chem. 86 (1982) 172–177. 5339–5343.
[6] A. Bard, M. Fox, Acc. Chem. Res. 28 (1995) 141–145. [67] X. Fu, X. Hu, Z. Yan, K. Lei, F. Li, F. Cheng, J. Chen, Chem. Commun. 52 (2016)
[7] X. Li, J. Yu, J. Low, Y. Fang, J. Xiao, X. Chen, J. Mater. Chem. A 3 (2015) 1725–1728.
2485–2534. [68] L. Zhao, L. Wang, P. Yu, D. Zhao, C. Tian, H. Feng, J. Ma, H. Fu, Chem. Commun.
[8] X. Chen, S. Shen, L. Guo, S.S. Mao, Chem. Rev. 110 (2010) 6503–6570. 51 (2015) 12399–12402.
[9] C. Chen, W. Ma, J. Zhao, Chem. Soc. Rev. 39 (2010) 4206–4219. [69] Y. Zheng, Y. Jiao, J. Chen, J. Liu, J. Liang, A. Du, W. Zhang, Z. Zhu, S.C. Smith, M.
[10] A. Kudo, Y. Miseki, Chem. Soc. Rev. 38 (2009) 253–278. Jaroniec, G.Q. Lu, S.Z. Qiao, J. Am. Chem. Soc. 133 (2011) 20116–20119.
[11] M. Hoffmann, S. Martin, W. Choi, D. Bahnemann, Chem. Rev. 95 (1995) [70] J. Yi, K. Liao, C. Zhang, T. Zhang, F. Li, H. Zhou, ACS Appl. Mater. Interfaces 7
69–96. (2015) 10823–10827.
[12] H. Zhang, G. Chen, D.W. Bahnemann, J. Mater. Chem. 19 (2009) 5089–5121. [71] Y. Liu, N. Li, S. Wu, K. Liao, K. Zhu, J. Yi, H. Zhou, Energy Environ. Sci. 8 (2015)
[13] M. Pelaez, N.T. Nolan, S.C. Pillai, M.K. Seery, P. Falaras, A.G. Kontos, P.S.M. 2664–2667.
Dunlop, J.W.J. Hamilton, J.A. Byrne, K. O’Shea, M.H. Entezari, D.D. Dionysiou, [72] Y. Hou, J.Y. Li, Z.H. Wen, S.M. Cui, C. Yuan, J.H. Chen, Nano Energy 8 (2014)
Appl. Catal. B: Environ. 125 (2012) 331–349. 157–164.
[14] C.C. Wang, J.R. Li, X.L. Lv, Y.Q. Zhang, G.S. Guo, Energy Environ. Sci. 7 (2014) [73] Y. Fu, J. Zhu, C. Hu, X. Wu, X. Wang, Nanoscale 6 (2014) 12555–12564.
2831–2867. [74] Y. Wu, T. Wang, Y. Zhang, S. Xin, X. He, D. Zhang, J. Shui, Sci. Rep. U. K. 6
[15] M.N. Chong, B. Jin, C.W.K. Chow, C. Saint, Water. Res. 44 (2010) 2997–3027. (2016) 24314.
[16] X. Li, J. Wen, J. Low, Y. Fang, J. Yu, Sci. China Mater. 57 (2014) 70–100. [75] W.-B. Luo, S.-L. Chou, J.-Z. Wang, Y.-C. Zhai, H.-K. Liu, Small 11 (2015)
[17] J. Low, J. Yu, W. Ho, J. Phys. Chem. Lett. 6 (2015) 4244–4251. 2817–2824.
[18] W. Tu, Y. Zhou, Z. Zou, Adv. Mater. 26 (2014) 4607–4626. [76] Q. Shang, Z. Zhou, Y. Shen, Y. Zhang, Y. Li, S. Liu, Y. Zhang, ACS Appl. Mater.
[19] M. Marszewski, S. Cao, J. Yu, M. Jaroniec, Mater. Horiz. 2 (2015) 261–278. Interfaces 7 (2015) 23672–23678.
[20] H. Park, Y. Park, W. Kim, W. Choi, J. Photochem. Photobiol. C 15 (2013) 1–20. [77] J. Zhuang, W. Lai, M. Xu, Q. Zhou, D. Tang, ACS Appl. Mater. Interfaces 7
[21] S. Malato, P. Fernandez-Ibanez, M.I. Maldonado, J. Blanco, W. Gernjak, Catal. (2015) 8330–8338.
Today 147 (2009) 1–59. [78] C. Cheng, Y. Huang, X. Tian, B. Zheng, Y. Li, H. Yuan, D. Xiao, S. Xie, M.M.F.
[22] Y. Shiraishi, T. Hirai, J. Photochem. Photobiol. C 9 (2008) 157–170. Choi, Anal. Chem. 84 (2012) 4754–4759.
[23] H. Kisch, Angew. Chem. Int. Ed. 52 (2013) 812–847. [79] M. Rong, L. Lin, X. Song, Y. Wang, Y. Zhong, J. Yan, Y. Feng, X. Zeng, X. Chen,
[24] X. Lang, X. Chen, J. Zhao, Chem. Soc. Rev. 43 (2014) 473–486. Biosens. Bioelectron. 68 (2015) 210–217.
[25] J. Wen, X. Li, W. Liu, Y. Fang, J. Xie, Y. Xu, Chin. J. Catal. 36 (2015) 2049–2070. [80] H. Huang, R. Chen, J. Ma, L. Yan, Y. Zhao, Y. Wang, W. Zhang, J. Fan, X. Chen,
[26] Q. Li, X. Li, S. Wageh, A.A. Al-Ghamdi, J. Yu, Adv. Energy Mater. 5 (2015) Chem. Commun. 50 (2014) 15415–15418.
1500010. [81] M.K. Kundu, M. Sadhukhan, S. Barman, J. Mater. Chem. B 3 (2015)
[27] S. Cao, J. Low, J. Yu, M. Jaroniec, Adv. Mater. 27 (2015) 2150–2176. 1289–1300.
[28] S. Cao, J. Yu, J. Phys. Chem. Lett. 5 (2014) 2101–2107. [82] T.Y. Ma, Y. Tang, S. Dai, S.Z. Qiao, Small 10 (2014) 2382–2389.
[29] A. Linsebigler, G. Lu, J. Yates Jr., Chem. Rev. 95 (1995) 735–758. [83] X. Li, J. Yu, M. Jaroniec, Chem. Soc. Rev. 45 (2016) 2603–2636.
[30] H. Tong, S.X. Ouyang, Y.P. Bi, N. Umezawa, M. Oshikiri, J.H. Ye, Adv. Mater. 24 [84] J. Zhang, X. Chen, K. Takanabe, K. Maeda, K. Domen, J.D. Epping, X. Fu, M.
(2012) 229–251. Antonietti, X. Wang, Angew. Chem. Int. Ed. 49 (2010) 441–444.
[31] A. Fujishima, T. Rao, D. Tryk, J. Photochem. Photobiol. C 1 (2000) 1–21. [85] X. Li, J. Yu, Heterogeneous Photocatalysis, in: J.C. Colmenares, Y.-J. Xu (Eds.),
[32] K. Nakata, A. Fujishima, J. Photochem. Photobiol. C 13 (2012) 169–189. Springer, Berlin Heidelberg, 2016, pp. 175–210.
[33] X. Chen, S.S. Mao, Chem. Rev. 107 (2007) 2891–2959. [86] X. Li, J. Low, J. Yu, Photocatalysis: Applications, in: G.L.P.D. Dionysios
[34] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science 293 (2001) Dionysiou, Jinhua Ye, Jenny Schneider, Detlef Bahnemann (Eds.), The Royal
269–271. Society of Chemistry, 2016, pp. 255–302.
[35] X.B. Chen, L. Liu, P.Y. Yu, S.S. Mao, Science 331 (2011) 746–750. [87] P.M. Wood, Biochem. J. 253 (1988) 287–289.
[36] S.U.M. Khan, M. Al-Shahry, W.B. Ingler, Science 297 (2002) 2243–2245. [88] J. Yang, D. Wang, H. Han, C. Li, Accounts. Chem. Res. 46 (2013) 1900–1909.
[37] X. Chen, C. Li, M. Gratzel, R. Kostecki, S.S. Mao, Chem. Soc. Rev. 41 (2012) [89] S. Chen, S. Shen, G. Liu, Y. Qi, F. Zhang, C. Li, Angew. Chem. Int. Ed. 54 (2015)
7909–7937. 3047–3051.
[38] L. Liu, X. Chen, Chem. Rev. 114 (2014) 9890–9918. [90] M.D. Ward, J.R. White, A.J. Bard, J. Am. Chem. Soc. 105 (1983) 27–31.
[39] Y. Ma, X. Wang, Y. Jia, X. Chen, H. Han, C. Li, Chem. Rev. 114 (2014) [91] P.E. de Jongh, D. Vanmaekelbergh, J.J. Kelly, Chem. Commun. (1999)
9987–10043. 1069–1070.
[40] X. Chen, L. Liu, F. Huang, Chem. Soc. Rev. 44 (2015) 1861–1885. [92] M.F. Finlayson, B.L. Wheeler, N. Kakuta, K.H. Park, A.J. Bard, A. Campion, M.A.
[41] A.J. Bard, J. Am. Chem. Soc. 132 (2010) 7559–7567. Fox, S.E. Webber, J.M. White, J. Phys. Chem. 89 (1985) 5676–5681.
[42] J. Xu, G. Wang, J. Fan, B. Liu, S. Cao, J. Yu, J. Power Sources 274 (2015) 77–84. [93] S.C. Yan, S.B. Lv, Z.S. Li, Z.G. Zou, Dalton Trans. 39 (2010) 1488–1491.
[43] J. Xu, T.J.K. Brenner, L. Chabanne, D. Neher, M. Antonietti, M. Shalom, J. Am. [94] W.-J. Chun, A. Ishikawa, H. Fujisawa, T. Takata, J.N. Kondo, M. Hara, M.
Chem. Soc. 136 (2014) 13486–13489. Kawai, Y. Matsumoto, K. Domen, J. Phys. Chem. B 107 (2003) 1798–1803.
[44] X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. Carlsson, K. Domen, M. [95] Cai Long, H. Kisch, J. Phys. Chem. C 112 (2008) 548–554.
Antonietti, Nat. Mater. 8 (2009) 76–80. [96] K.L. Hardee, A.J. Bard, J. Electrochem. Soc. 124 (1977) 215–224.
[45] G. Dong, Y. Zhang, Q. Pan, J. Qiu, J. Photochem. Photobiol. C 20 (2014) 33–50. [97] Z.G. Yi, J.H. Ye, N. Kikugawa, T. Kako, S.X. Ouyang, H. Stuart-Williams, H.
[46] X.-H. Li, M. Antonietti, Chem. Soc. Rev. 42 (2013) 6593–6604. Yang, J.Y. Cao, W.J. Luo, Z.S. Li, Y. Liu, R.L. Withers, Nat. Mater. 9 (2010)
[47] Y. Wang, X. Wang, M. Antonietti, Angew. Chem. Int. Ed. 51 (2012) 68–89. 559–564.
[48] Y. Zheng, J. Liu, J. Liang, M. Jaroniec, S.Z. Qiao, Energy Environ. Sci. 5 (2012) [98] A.J. Bard, R. Parsons, J. Jordan, Standard Potentials in Aqueous Solution, CRC
6717–6731. Press, 1985.
[49] J. Zhu, P. Xiao, H. Li, S.A.C. Carabineiro, ACS Appl. Mater. Interfaces 6 (2014) [99] Y. Gong, M. Li, Y. Wang, ChemSusChem 8 (2015) 931–946.
16449–16465. [100] X. Zhang, X. Xie, H. Wang, J. Zhang, B. Pan, Y. Xie, J. Am. Chem. Soc. 135
[50] S. Ye, R. Wang, M.-Z. Wu, Y.-P. Yuan, Appl. Surf. Sci. 358 (2015) 15–27. (2013) 18–21.
[51] S. Yin, J. Han, T. Zhou, R. Xu, Catal. Sci. Technol. 5 (2015) 5048–5061. [101] A. Thomas, A. Fischer, F. Goettmann, M. Antonietti, J.-O. Muller, R. Schlogl,
[52] J. Zhang, Y. Chen, X. Wang, Energy Environ. Sci. 8 (2015) 3092–3108. J.M. Carlsson, J. Mater. Chem. 18 (2008) 4893–4908.
[53] Z. Zhao, Y. Sun, F. Dong, Nanoscale 7 (2015) 15–37.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 115

[102] M.J. Bojdys, J.-O. Mueller, M. Antonietti, A. Thomas, Chem. Eur. J. 14 (2008) [148] F. Dong, L. Wu, Y. Sun, M. Fu, Z. Wu, S.C. Lee, J. Mater. Chem. 21 (2011)
8177–8182. 15171–15174.
[103] K. Schwinghammer, M.B. Mesch, V. Duppel, C. Ziegler, J. Senker, B.V. Lotsch, [149] S.C. Yan, Z.S. Li, Z.G. Zou, Langmuir 25 (2009) 10397–10401.
J. Am. Chem. Soc. 136 (2014) 1730–1733. [150] J. Zhang, M. Zhang, G. Zhang, X. Wang, ACS Catal. 2 (2012) 940–948.
[104] W.-r. Lee, Y.-S. Jun, J. Park, G.D. Stucky, J. Mater. Chem. A 3 (2015) [151] Q. Xiang, J. Yu, M. Jaroniec, J. Phys. Chem. C 115 (2011) 7355–7363.
24232–24236. [152] P. Wang, Z. Wang, L. Jia, Z. Xiao, Phys. Chem. Chem. Phys. 11 (2009)
[105] G. Algara-Siller, N. Severin, S.Y. Chong, T. Bjorkman, R.G. Palgrave, A. 2730–2740.
Laybourn, M. Antonietti, Y.Z. Khimyak, A.V. Krasheninnikov, J.P. Rabe, U. [153] F. Dong, Z. Wang, Y. Sun, W.-K. Ho, H. Zhang, J. Colloid Interface Sci. 401
Kaiser, A.I. Cooper, A. Thomas, M.J. Bojdys, Angew. Chem. Int. Ed. 53 (2014) (2013) 70–79.
7450–7455. [154] J. Jiang, O.-y. Lei, L. Zhu, A. Zheng, J. Zou, X. Yi, H. Tang, Carbon 80 (2014)
[106] H. Gao, S. Yan, J. Wang, Y.A. Huang, P. Wang, Z. Li, Z. Zou, Phys. Chem. Chem. 213–221.
Phys. 15 (2013) 18077–18084. [155] G. Bi, J. Wen, X. Li, W. Liu, J. Xie, Y. Fang, W. Zhang, RSC Adv. 6 (2016)
[107] Y.-S. Jun, E.Z. Lee, X. Wang, W.H. Hong, G.D. Stucky, A. Thomas, Adv. Funct. 31497–31506.
Mater. 23 (2013) 3661–3667. [156] J. Wen, X. Li, H. Li, S. Ma, K. He, Y. Xu, Y. Fang, W. Liu, Q. Gao, Appl. Surf. Sci.
[108] M.K. Bhunia, K. Yamauchi, K. Takanabe, Angew. Chem. Int. Ed. 53 (2014) 358 (2015) 204–212.
11001–11005. [157] T. Yan, H. Chen, X. Wang, F. Jiang, RSC Adv. 3 (2013) 22480–22489.
[109] M. Shalom, S. Gimenez, F. Schipper, I. Herraiz-Cardona, J. Bisquert, M. [158] Y.J. Zhang, A. Thomas, M. Antonietti, X.C. Wang, J. Am. Chem. Soc. 131 (2009)
Antonietti, Angew. Chem. Int. Ed. 53 (2014) 3654–3658. 50.
[110] M. Shalom, S. Inal, C. Fettkenhauer, D. Neher, M. Antonietti, J. Am. Chem. Soc. [159] Y. Zhong, Z. Wang, J. Feng, S. Yan, H. Zhang, Z. Li, Z. Zou, Appl. Surf. Sci. 295
135 (2013) 7118–7121. (2014) 253–259.
[111] Y. Ishida, L. Chabanne, M. Antonietti, M. Shalom, Langmuir 30 (2014) [160] W.-J. Ong, L.-L. Tan, S.-P. Chai, S.-T. Yong, A.R. Mohamed, Nano Energy 13
447–451. (2015) 757–770.
[112] Y.-P. Yuan, L.-S. Yin, S.-W. Cao, L.-N. Gu, G.-S. Xu, P. Du, H. Chai, Y.-S. Liao, C. [161] C. Ye, J.-X. Li, Z.-J. Li, X.-B. Li, X.-B. Fan, L.-P. Zhang, B. Chen, C.-H. Tung, L.-Z.
Xue, Green Chem. 16 (2014) 4663–4668. Wu, ACS Catal. 5 (2015) 6973–6979.
[113] L. Lin, P. Ye, C. Cao, Q. Jin, G.-S. Xu, Y.-H. Shen, Y.-P. Yuan, J. Mater. Chem. A 3 [162] Y. Xu, M. Xie, S. Huang, H. Xu, H. Ji, J. Xia, Y. Li, H. Li, RSC Adv. 5 (2015)
(2015) 10205–10208. 26281–26290.
[114] Y. Wang, J. Zhang, X. Wang, M. Antonietti, H. Li, Angew. Chem. Int. Ed. 49 [163] X.-j. Wang, X. Tian, F.-t. Li, Y.-p. Li, J. Zhao, Y.-j. Hao, Y. Liu, Int. J. Hydrogen
(2010) 3356–3359. Energy 41 (2016) 3888–3895.
[115] L. Xu, J. Xia, H. Xu, S. Yin, K. Wang, L. Huang, L. Wang, H. Li, J. Power Sources [164] T. Sano, S. Tsutsui, K. Koike, T. Hirakawa, Y. Teramoto, N. Negishi, K.
245 (2014) 866–874. Takeuchi, J. Mater. Chem. A 1 (2013) 6489–6496.
[116] J. Di, J. Xia, S. Yin, H. Xu, M. He, H. Li, L. Xu, Y. Jiang, RSC Adv. 3 (2013) [165] H. Nie, M. Ou, Q. Zhong, S. Zhang, L. Yu, J. Hazard. Mater. 300 (2015) 598–606.
19624–19631. [166] X.L. Wang, W.Q. Fang, H.F. Wang, H. Zhang, H. Zhao, Y. Yao, H.G. Yang, J.
[117] J. Di, J. Xia, S. Yin, H. Xu, L. Xu, Y. Xu, M. He, H. Li, J. Mater. Chem. A 2 (2014) Mater. Chem. A 1 (2013) 14089–14096.
5340–5351. [167] E.G. Gillan, Chem. Mater. 12 (2000) 3906–3912.
[118] J. Zhang, J. Sun, K. Maeda, K. Domen, P. Liu, M. Antonietti, X. Fu, X. Wang, [168] D.R. Miller, J. Wang, E.G. Gillan, J. Mater. Chem. 12 (2002) 2463–2469.
Energy Environ. Sci. 4 (2011) 675–678. [169] Y. Li, J. Zhang, Q. Wang, Y. Jin, D. Huang, Q. Cui, G. Zou, J. Phys. Chem. B 114
[119] F. Su, S.C. Mathew, G. Lipner, X. Fu, M. Antonietti, S. Blechert, X. Wang, J. Am. (2010) 9429–9434.
Chem. Soc. 132 (2010) 16299–16301. [170] Y. Cui, J. Zhang, G. Zhang, J. Huang, P. Liu, M. Antonietti, X. Wang, J. Mater.
[120] Y. Hou, A.B. Laursen, J. Zhang, G. Zhang, Y. Zhu, X. Wang, S. Dahl, I. Chem. 21 (2011) 13032–13039.
Chorkendorff, Angew. Chem. Int. Ed. 52 (2013) 3621–3625. [171] T. Komatsu, T. Nakamura, J. Mater. Chem. 11 (2001) 474–478.
[121] J. Zhang, M. Zhang, R.-Q. Sun, X. Wang, Angew. Chem. Int. Ed. 51 (2012) [172] Y. Yuan, L. Zhang, J. Xing, M.I.B. Utama, X. Lu, K. Du, Y. Li, X. Hu, S. Wang, A.
10145–10149. Genc, R. Dunin-Borkowski, J. Arbiol, Q. Xiong, Nanoscale 7 (2015)
[122] X. Chen, Y.-S. Jun, K. Takanabe, K. Maeda, K. Domen, X. Fu, M. Antonietti, X. 12343–12350.
Wang, Chem. Mater. 21 (2009) 4093–4095. [173] L. Shi, L. Liang, F. Wang, J. Ma, J. Sun, Catal. Sci. Technol. 4 (2014) 3235–3243.
[123] X.C. Wang, K. Maeda, X.F. Chen, K. Takanabe, K. Domen, Y.D. Hou, X.Z. Fu, M. [174] A. Fischer, M. Antonietti, A. Thomas, Adv. Mater. 19 (2007) 264–267.
Antonietti, J. Am. Chem. Soc. 131 (2009) 1680–1681. [175] Q. Gao, S. Wang, Y. Ma, Y. Tang, C. Giordano, M. Antonietti, Angew. Chem.
[124] J. Ran, J. Zhang, J. Yu, M. Jaroniec, S.Z. Qiao, Chem. Soc. Rev. 43 (2014) Int. Ed. 51 (2012) 961–965.
7787–7812. [176] X.-H. Li, M. Antonietti, Angew. Chem. Int. Ed. 52 (2013) 4572–4576.
[125] J. Hong, Y. Wang, Y. Wang, W. Zhang, R. Xu, ChemSusChem 6 (2013) [177] A. Fischer, J.O. Mueller, M. Antonietti, A. Thomas, ACS Nano 2 (2008)
2263–2268. 2489–2496.
[126] J. Yu, S. Wang, B. Cheng, Z. Lin, F. Huang, Catal. Sci. Technol. 3 (2013) [178] J. Xu, L. Zhang, R. Shi, Y. Zhu, J. Mater. Chem. A 1 (2013) 14766–14772.
1782–1789. [179] J. Zhang, M. Zhang, L. Lin, X. Wang, Angew. Chem. Int. Ed. 54 (2015)
[127] D.M. Teter, R.J. Hemley, Science 271 (1996) 53–55. 6297–6301.
[128] G. Zhang, M. Zhang, X. Ye, X. Qiu, S. Lin, X. Wang, Adv. Mater. 26 (2014) [180] Z. Zhou, J. Wang, J. Yu, Y. Shen, Y. Li, A. Liu, S. Liu, Y. Zhang, J. Am. Chem. Soc.
805–809. 137 (2015) 2179–2182.
[129] M. Zhang, X. Wang, Energy Environ. Sci. 7 (2014) 1902–1906. [181] Y. Zhang, M. Antonietti, Chem. Asian. J. 5 (2010) 1307–1311.
[130] J. Zhang, G. Zhang, X. Chen, S. Lin, L. Moehlmann, G. Dolega, G. Lipner, M. [182] H. Jindui, X. Xiaoyang, W. Yongsheng, X. Rong, J. Mater. Chem. 22 (2012)
Antonietti, S. Blechert, X. Wang, Angew. Chem. Int. Ed. 51 (2012) 3183–3187. 15006–15012.
[131] Y. Xu, S.-P. Gao, Int. J. Hydrogen Energy 37 (2012) 11072–11080. [183] S. Guo, Z. Deng, M. Li, B. Jiang, C. Tian, Q. Pan, H. Fu, Angew. Chem. Int. Ed. 55
[132] A.Y. Liu, M.L. Cohen, Science 245 (1989) 841–842. (2016) 1830–1834.
[133] K. Maeda, X. Wang, Y. Nishihara, D. Lu, M. Antonietti, K. Domen, J. Phys. [184] J. Li, B. Shen, Z. Hong, B. Lin, B. Gao, Y. Chen, Chem. Commun. 48 (2012)
Chem. C 113 (2009) 4940–4947. 12017–12019.
[134] B. Jürgens, E. Irran, J. Senker, P. Kroll, H. Müller, W. Schnick, J. Am. Chem. Soc. [185] G. Dong, K. Zhao, L. Zhang, Chem. Commun. 48 (2012) 6178–6180.
125 (2003) 10288–10300. [186] Q. Han, C. Hu, F. Zhao, Z. Zhang, N. Chen, L. Qu, J. Mater. Chem. A 3 (2015)
[135] J. Sehnert, K. Baerwinkel, J. Senker, J. Phys. Chem. B 111 (2007) 4612–4619.
10671–10680. [187] X. Wang, S. Blechert, M. Antonietti, ACS Catal. 2 (2012) 1596–1606.
[136] E. Kroke, M. Schwarz, E. Horath-Bordon, P. Kroll, B. Noll, A.D. Norman, New J. [188] M.K. Bhunia, S. Melissen, M.R. Parida, P. Sarawade, J.-M. Basset, D.H. Anjum,
Chem. 26 (2002) 508–512. O.F. Mohammed, P. Sautet, T. Le Bahers, K. Takanabe, Chem. Mater. 27
[137] M.J. McAllister, J.-L. Li, D.H. Adamson, H.C. Schniepp, A.A. Abdala, J. Liu, M. (2015) 8237–8247.
Herrera-Alonso, D.L. Milius, R. Car, R.K. Prud’homme, I.A. Aksay, Chem. [189] M. Lan, G. Fan, L. Yang, F. Li, RSC Adv. 5 (2015) 5725–5734.
Mater. 19 (2007) 4396–4404. [190] T. Dittrich, S. Fiechter, A. Thomas, Appl. Phys. Lett. 99 (2011) 084105.
[138] J. Gao, Y. Zhou, Z. Li, S. Yan, N. Wang, Z. Zou, Nanoscale 4 (2012) 3687–3692. [191] P. Wu, J. Wang, J. Zhao, L. Guo, F.E. Osterloh, J. Mater. Chem. A 2 (2014)
[139] E. Haque, J.W. Jun, S.N. Talapaneni, A. Vinu, S.H. Jhung, J. Mater. Chem. 20 20338–20344.
(2010) 10801–10803. [192] L. Bi, D. Xu, L. Zhang, Y. Lin, D. Wang, T. Xie, Phys. Chem. Chem. Phys. 17
[140] S.Y. Kim, J. Oh, S. Park, Y. Shim, S. Park, Chem. Eur. J. 22 (2016) 5142–5145. (2015) 29899–29905.
[141] J. Liu, W. Li, L. Duan, X. Li, L. Ji, Z. Geng, K. Huang, L. Lu, L. Zhou, Z. Liu, W. [193] C. Han, Y. Lu, J. Zhang, L. Ge, Y. Li, C. Chen, Y. Xin, L. Wu, S. Fang, J. Mater.
Chen, L. Liu, S. Feng, Y. Zhang, Nano Lett. 15 (2015) 5137–5142. Chem. A 3 (2015) 23274–23282.
[142] J. Oh, R.J. Yoo, S.Y. Kim, Y.J. Lee, D.W. Kim, S. Park, Chem. Eur. J. 21 (2015) [194] C. Han, L. Wu, L. Ge, Y. Li, Z. Zhao, Carbon 92 (2015) 31–40.
6241–6246. [195] F. Dong, P. Li, J. Zhong, X. Liu, Y. Zhang, W. Cen, H. Huang, Appl. Catal. A-Gen.
[143] L. Ming, H. Yue, L. Xu, F. Chen, J. Mater. Chem. A 2 (2014) 19145–19149. 510 (2016) 161–170.
[144] G. Dong, Z. Ai, L. Zhang, RSC Adv. 4 (2014) 5553–5560. [196] T. Tyborski, C. Merschjann, S. Orthmann, F. Yang, M.C. Lux-Steiner, S.-N. Th,
[145] H.-J. Li, B.-W. Sun, L. Sui, D.-J. Qian, M. Chen, Phys. Chem. Chem. Phys. 17 J. Phys.: Condens. Matter 24 (2012) 162201.
(2015) 3309–3315. [197] J. Yuan, J. Wen, Y. Zhong, X. Li, Y. Fang, S. Zhang, W. Liu, J. Mater. Chem. A 3
[146] B. Zhu, P. Xia, W. Ho, J. Yu, Appl. Surf. Sci. 344 (2015) 188–195. (2015) 18244–18255.
[147] Y. Chen, J. Li, Z. Hong, B. Shen, B. Lin, B. Gao, Phys. Chem. Chem. Phys. 16 [198] Y. Zhong, J. Yuan, J. Wen, X. Li, Y. Xu, W. Liu, S. Zhang, Y. Fang, Dalton Trans.
(2014) 8106–8113. 44 (2015) 18260–18269.
116 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

[199] K. Wang, Q. Li, B. Liu, B. Cheng, W. Ho, J. Yu, Appl. Catal. B: Environ. 176–177 [257] T. Yang, J. Liu, R. Zhou, Z.G. Chen, H. Xu, S. Qiao, M. Monteiro, J. Mater. Chem.
(2015) 44–52. A 2 (2014) 18139–18146.
[200] J. Jiang, J. Yu, S. Cao, J. Colloid Interface Sci. 461 (2016) 56–63. [258] S. Chen, J. Bi, Y. Zhao, L. Yang, C. Zhang, Y. Ma, Q. Wu, X. Wang, Z. Hu, Adv.
[201] L. Yuan, C. Han, M. Pagliaro, Y.J. Xu, J. Phys. Chem. C 120 (2016) 265–273. Mater. 24 (2012) 5593–5597.
[202] Y. Zhang, Q. Pan, G. Chai, M. Liang, G. Dong, Q. Zhang, J. Qiu, Sci. Rep. U. K. 3 [259] Q. Mi, D. Chen, J. Hu, Z. Huang, J. Li, Chin. J. Catal. 34 (2013) 2138–2145.
(2013) 1943. [260] K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Science 323 (2009) 760–764.
[203] Z. Zhou, Y. Shen, Y. Li, A. Liu, S. Liu, Y. Zhang, ACS Nano 9 (2015) [261] L. Qu, Y. Liu, J.-B. Baek, L. Dai, ACS Nano 4 (2010) 1321–1326.
12480–12487. [262] J. Tian, Q. Liu, A.M. Asiri, K.A. Alamry, X. Sun, ChemSusChem 7 (2014)
[204] N.Y. Liu, J. Liu, W.Q. Kong, H. Li, H. Huang, Y. Liu, Z.H. Kang, J. Mater. Chem. B 2125–2130.
2 (2014) 5768–5774. [263] J. Tian, R. Ning, Q. Liu, A.M. Asiri, A.O. Al-Youbi, X. Sun, ACS Appl. Mater.
[205] Y.-C. Lu, J. Chen, A.-J. Wang, N. Bao, J.-J. Feng, W. Wang, L. Shao, J. Mater. Interfaces 6 (2014) 1011–1017.
Chem. C 3 (2015) 73–78. [264] S.S. Shinde, A. Sami, J.-H. Lee, ChemCatChem 7 (2015) 3873–3880.
[206] L. Chen, D. Huang, S. Ren, T. Dong, Y. Chi, G. Chen, Nanoscale 5 (2013) [265] Y. Qin, J. Li, J. Yuan, Y. Kong, Y. Tao, F. Lin, S. Li, J. Power Sources 272 (2014)
225–230. 696–702.
[207] Y. Feng, Q. Wang, J. Lei, H. Ju, Biosens. Bioelectron. 73 (2015) 7–12. [266] Q. Liu, J. Zhang, Langmuir 29 (2013) 3821–3828.
[208] S. Zhang, J. Li, M. Zeng, J. Xu, X. Wang, W. Hu, Nanoscale 6 (2014) 4157–4162. [267] J. Jin, X. Fu, Q. Liu, J. Zhang, J. Mater. Chem. A 1 (2013) 10538–10545.
[209] Z. Yang, M. Xu, Y. Liu, F. He, F. Gao, Y. Su, H. Wei, Y. Zhang, Nanoscale 6 [268] E. Negro, S. Polizzi, K. Vezzu, L. Toniolo, G. Cavinato, V. Di Noto, Int. J.
(2014) 1890–1895. Hydrogen Energy 39 (2014) 2828–2841.
[210] X. Qin, W. Lu, A.M. Asiri, A.O. Al-Youbi, X. Sun, Catal. Sci. Technol. 3 (2013) [269] E. Negro, K. Vezzu, F. Bertasi, P. Schiavuta, L. Toniolo, S. Polizzi, V. Di Noto,
1027–1035. ChemElectroChem 1 (2014) 1359–1369.
[211] X. Li, Z. Li, Q. Xia, H. Xi, Z. Zhao, Adsorpt. Sci. Technol. 24 (2006) 363–374. [270] M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q. Mi, E.A. Santori,
[212] X. Li, Z. Li, Q. Xia, H. Xi, Appl. Therm. Eng. 27 (2007) 869–876. N.S. Lewis, Chem. Rev. 110 (2010) 6446–6473.
[213] X. Li, Z. Li, J. Chem. Eng. Data 55 (2010) 5729–5732. [271] F. Wen, C. Li, Acc. Chem. Res. 46 (2013) 2355–2364.
[214] X. Li, H. Li, S. Huo, Z. Li, Kinet. Catal. 51 (2010) 754–761. [272] Y. Xu, R. Xu, Appl. Surf. Sci. 351 (2015) 779–793.
[215] X. Li, X. Chen, Z. Li, J. Chem. Eng. Data 55 (2010) 3164–3169. [273] M.S. Faber, S. Jin, Energy Environ. Sci. 7 (2014) 3519–3542.
[216] R.K. Upadhyay, N. Soin, S.S. Roy, RSC Adv. 4 (2014) 3823–3851. [274] P. Du, R. Eisenberg, Energy Environ. Sci. 5 (2012) 6012–6021.
[217] S. Liu, J. Yu, M. Jaroniec, J. Am. Chem. Soc. 132 (2010) 11914–11916. [275] X. Zou, Y. Zhang, Chem. Soc. Rev. 44 (2015) 5148–5180.
[218] Q. Xiang, J. Yu, M. Jaroniec, Chem. Commun. 47 (2011) 4532–4534. [276] A. Du, S. Sanvito, Z. Li, D. Wang, Y. Jiao, T. Liao, Q. Sun, Y.H. Ng, Z. Zhu, R.
[219] S. Liu, C. Liu, W. Wang, B. Cheng, J. Yu, Nanoscale 4 (2012) 3193–3200. Amal, S.C. Smith, J. Am. Chem. Soc. 134 (2012) 4393–4397.
[220] F. Wu, W. Liu, J. Qiu, J. Li, W. Zhou, Y. Fang, S. Zhang, X. Li, Appl. Surf. Sci. 358 [277] Y. Zhao, F. Zhao, X. Wang, C. Xu, Z. Zhang, G. Shi, L. Qu, Angew. Chem. Int. Ed.
(2015) 425–435. 53 (2014) 13934–13939.
[221] C. Shen, C. Chen, T. Wen, Z. Zhao, X. Wang, A. Xu, J. Colloid Interface Sci. 456 [278] X. Zou, R. Silva, A. Goswami, T. Asefa, Appl. Surf. Sci. 357 (2015) 221–228.
(2015) 7–14. [279] Y. Zhang, Z. Schnepp, J. Cao, S. Ouyang, Y. Li, J. Ye, S. Liu, Sci. Rep. U. K. 3
[222] R.G. Pearson, J. Am. Chem. Soc. 85 (1963) 3533–3539. (2013) 2163.
[223] R.G. Parr, R.G. Pearson, J. Am. Chem. Soc. 105 (1983) 7512–7516. [280] F. Yang, V. Kuznietsov, M. Lublow, C. Merschjann, A. Steigert, J. Klaer, A.
[224] M. Yu, Z. Li, Q. Xia, H. Xi, S. Wang, Chem. Eng. J. 132 (2007) 233–239. Thomas, T. Schedel-Niedrig, J. Mater. Chem. A 1 (2013) 6407–6415.
[225] A. Alfarra, E. Frackowiak, F. Béguin, Appl. Surf. Sci. 228 (2004) 84–92. [281] Y. Li, R. Wang, H. Li, X. Wei, J. Feng, K. Liu, Y. Dang, A. Zhou, J. Phys. Chem. C
[226] Y. Oh, V.-D. Le, U.N. Maiti, J.O. Hwang, W.J. Park, J. Lim, K.E. Lee, Y.-S. Bae, 119 (2015) 20283–20292.
Y.-H. Kim, S.O. Kim, ACS Nano 9 (2015) 9148–9157. [282] M. Yang, J. Liu, X. Zhang, S. Qiao, H. Huang, Y. Liu, Z. Kang, Phys. Chem. Chem.
[227] Q. Huang, J. Yu, S. Cao, C. Cui, B. Cheng, Appl. Surf. Sci. 358 (2015) 350–355. Phys. 17 (2015) 17887–17893.
[228] L. Jia, H. Wang, D. Dhawale, C. Anand, M.A. Wahab, Q. Ji, K. Ariga, A. Vinu, [283] X. Zhou, F. Peng, H. Wang, H. Yu, Y. Fang, Chem. Commun. 47 (2011)
Chem. Commun. 50 (2014) 5976–5979. 10323–10325.
[229] Q. Li, J. Yang, D. Feng, Z. Wu, Q. Wu, S.S. Park, C.-S. Ha, D. Zhao, Nano Res. 3 [284] Y. Li, X. Wei, H. Li, R. Wang, J. Feng, H. Yun, A. Zhou, RSC Adv. 5 (2015)
(2010) 632–642. 14074–14080.
[230] X. Xu, C. Song, J.M. Andrésen, B.G. Miller, A.W. Scaroni, Microporous [285] Y. Hou, F. Zuo, A.P. Dagg, J. Liu, P. Feng, Adv. Mater. 26 (2014) 5043–5049.
Mesoporous Mater. 62 (2003) 29–45. [286] F. Zhan, R. Xie, W. Li, J. Li, Y. Yang, Y. Li, Q. Chen, RSC Adv. 5 (2015)
[231] X. Xu, C. Song, J.M. Andresen, B.G. Miller, A.W. Scaroni, Energy Fuel 16 69753–69760.
(2002) 1463–1469. [287] Y. Li, X. Wei, X. Yan, J. Cai, A. Zhou, M. Yang, K. Liu, Phys. Chem. Chem. Phys.
[232] X. Ma, X. Wang, C. Song, J. Am. Chem. Soc. 131 (2009) 5777–5783. 18 (2016) 10255–10261.
[233] Z. Zhang, M. Xu, H. Wang, Z. Li, Chem. Eng. J. 160 (2010) 571–577. [288] Y. Hou, Z. Wen, S. Cui, X. Feng, J. Chen, Nano Lett. 16 (2016) 2268–2277.
[234] Z. Zhang, Y. Zhao, Q. Gong, Z. Li, J. Li, Chem. Commun. 49 (2013) 653–661. [289] Y. Liu, Y.-X. Yu, W.-D. Zhang, Int. J. Hydrogen Energy 39 (2014) 9105–9113.
[235] Z. Zhang, Z. Li, J. Li, Langmuir 28 (2012) 12122–12133. [290] L. Ye, D. Wang, S. Chen, ACS Appl. Mater. Interfaces 8 (2016) 5280–5289.
[236] Z. Zhang, S. Huang, S. Xian, H. Xi, Z. Li, Energy Fuel 25 (2011) 835–842. [291] P.-Y. Kuang, Y.-Z. Su, G.-F. Chen, Z. Luo, S.-Y. Xing, N. Li, Z.-Q. Liu, Appl. Surf.
[237] S. Liu, J. Xia, J. Yu, ACS Appl. Mater. Interfaces 7 (2015) 8166–8175. Sci. 358 (2015) 296–303.
[238] S.M. Lyth, Y. Nabae, S. Moriya, S. Kuroki, M.-a. Kakimoto, J.-i. Ozaki, S. [292] J. Yan, Z. Chen, H. Ji, Z. Liu, X. Wang, Y. Xu, X. She, L. Huang, L. Xu, H. Xu, H. Li,
Miyata, J. Phys. Chem. C 113 (2009) 20148–20151. Chem. Eur. J. 22 (2016) 4764–4773.
[239] Y. Zheng, Y. Jiao, Y. Zhu, L.H. Li, Y. Han, Y. Chen, A. Du, M. Jaroniec, S.Z. Qiao, [293] F. Liang, Y. Zhu, Appl. Catal. B: Environ. 180 (2016) 324–329.
Nat. Commun. 5 (2014) 3783. [294] J. Wang, W.-D. Zhang, Electrochim. Acta 71 (2012) 10–16.
[240] J.J. Li, Y.M. Zhang, X.H. Zhang, J.C. Han, Y. Wang, L. Gu, Z.H. Zhang, X.J. Wang, [295] L. Liu, G. Zhang, J.T.S. Irvine, Y. Wu, Energy Technol. 3 (2015) 982–988.
J.K. Jian, P. Xu, B. Song, ACS Appl. Mater. Interfaces 7 (2015) 19626–19634. [296] Z. Mo, X. She, Y. Li, L. Liu, L. Huang, Z. Chen, Q. Zhang, H. Xu, H. Li, RSC Adv. 5
[241] M.K. Kundu, T. Bhowmik, S. Barman, J. Mater. Chem. A 3 (2015) (2015) 101552–101562.
23120–23135. [297] H. Gao, S. Yan, J. Wang, Z. Zou, Dalton Trans. 43 (2014) 8178–8183.
[242] Y. Xu, M. Kraft, R. Xu, Chem. Soc. Rev. 45 (2016) 3039–3052. [298] X. Wang, X. Chen, A. Thomas, X. Fu, M. Antonietti, Adv. Mater. 21 (2009)
[243] H. Tada, Q. Jin, A. Iwaszuk, M. Nolan, J. Phys. Chem. C 118 (2014) 1609–1612.
12077–12086. [299] J. Tian, Q. Liu, A.M. Asiri, A.H. Qusti, A.O. Al-Youbi, X. Sun, Nanoscale 5 (2013)
[244] X.-H. Li, J.-S. Chen, X. Wang, J. Sun, M. Antonietti, J. Am. Chem. Soc. 133 11604–11609.
(2011) 8074–8077. [300] B. Yue, Q. Li, H. Iwai, T. Kako, J. Ye, Sci. Technol. Adv. Mater. 12 (2011)
[245] Z. Ding, X. Chen, M. Antonietti, X. Wang, ChemSusChem 4 (2011) 274–281. 034401.
[246] L. Nie, P. Zhou, J. Yu, M. Jaroniec, J. Mol. Catal. A: Chem. 390 (2014) 7–13. [301] S. Hu, R. Jin, G. Lu, D. Liu, J. Gui, RSC Adv. 4 (2014) 24863–24869.
[247] C. Yu, J. Chen, F. Cao, X. Li, Q. Fan, J.C. Yu, L. Wei, Chin. J. Catal. 34 (2013) [302] S. Tonda, S. Kumar, S. Kandula, V. Shanker, J. Mater. Chem. A 2 (2014)
385–390. 6772–6780.
[248] L. Zhang, Y. Li, Q. Zhang, H. Wang, Appl. Surf. Sci. 319 (2014) 21–28. [303] Z. Li, C. Kong, G. Lu, J. Phys. Chem. C 120 (2016) 56–63.
[249] J. Yu, L. Yue, S. Liu, B. Huang, X. Zhang, J. Colloid Interface Sci. 334 (2009) [304] H. Pan, Y.-W. Zhang, V.B. Shenoy, H. Gao, ACS Catal. 1 (2011) 99–104.
58–64. [305] M. Zhang, X. Bai, D. Liu, J. Wang, Y. Zhu, Appl. Catal. B: Environ. 164 (2015)
[250] C. Yu, G. Li, S. Kumar, H. Kawasaki, R. Jin, J. Phys. Chem. Lett. 4 (2013) 77–81.
2847–2852. [306] T. Xiong, W.L. Cen, Y.X. Zhang, F. Dong, ACS Catal. 6 (2016) 2462–2472.
[251] J. Yu, J. Xiong, B. Cheng, S. Liu, Appl. Catal. B: Environ. 60 (2005) 211–221. [307] L. Ge, C. Han, X. Xiao, L. Guo, Y. Li, Mater. Res. Bull. 48 (2013) 3919–3925.
[252] B. Cheng, Y. Le, J. Yu, J. Hazard. Mater. 177 (2010) 971–977. [308] S. Stolbov, S. Zuluaga, J. Phys. Condens. Matter 25 (2013) 085507.
[253] J. Liang, Y. Jiao, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. Ed. 51 (2012) [309] F. Liang-Liang, Z. Yongcun, L. Chunguang, G. Shuang, Z. Li-Jing, S. Qiushi, F.
11496–11500. Meihong, W. Huijie, W. Dejun, L. Guo-Dong, Z. Xiaoxin, Int. J. Hydrogen
[254] Y. Zheng, Y. Jiao, L. Ge, M. Jaroniec, S.Z. Qiao, Angew. Chem. Int. Ed. 52 (2013) Energy 39 (2014) 15373–15379.
3110–3116. [310] C. Wang, Y. Guo, Y. Yang, S. Chu, C. Zhou, Y. Wang, Z. Zou, ACS Appl. Mater.
[255] J. Liang, X. Du, C. Gibson, X.W. Du, S.Z. Qiao, Adv. Mater. 25 (2013) Interfaces 6 (2014) 4321–4328.
6226–6231. [311] L. Cao, R. Wang, D.X. Wang, Mater. Lett. 149 (2015) 50–53.
[256] J. Duan, S. Chen, S. Dai, S.Z. Qiao, Adv. Funct. Mater. 24 (2014) 2072–2078. [312] Y.J. Zhang, T. Mori, J.H. Ye, M. Antonietti, J. Am. Chem. Soc. 132 (2010)
6294–6295.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 117

[313] Z. Ligang, C. Xiufang, G. Jing, J. Yijun, H. Tonggang, M. Xindong, Mater. Res. [365] Y. Zheng, L. Lin, X. Ye, F. Guo, X. Wang, Angew. Chem. Int. Ed. 53 (2014)
Bull. 48 (2013) 3485–3491. 11926–11930.
[314] J. Luo, X. Zhou, L. Ma, X. Xu, RSC Adv. 5 (2015) 68728–68735. [366] J. Liu, J. Huang, H. Zhou, M. Antonietti, ACS Appl. Mater. Interfaces 6 (2014)
[315] Y.P. Zhu, T.Z. Ren, Z.Y. Yuana, ACS Appl. Mater. Interfaces 7 (2015) 8434–8440.
16850–16856. [367] S.C. Lee, H.O. Lintang, L. Yuliati, Chem. Asian J. 7 (2012) 2139–2144.
[316] J.J. Liu, J. Alloy Compd. 672 (2016) 271–276. [368] E.Z. Lee, Y.-S. Jun, W.H. Hong, A. Thomas, M.M. Jin, Angew. Chem. Int. Ed. 49
[317] C. Lu, R. Chen, X. Wu, M. Fan, Y. Liu, Z. Le, S. Jiang, S. Song, Appl. Surf. Sci. 360 (2010) 9706–9710.
(2016) 1016–1022. [369] Z. Jinshui, Z. Mingwen, Y. Can, W. Xinchen, Adv. Mater. 26 (2014)
[318] T. Bharathidasan, A. Mandalam, M. Balasubramanian, P. Dhandapani, S. 4121–4126.
Sathiyanarayanan, S. Mayavan, ACS Appl. Mater. Interfaces 7 (2015) [370] J. Wang, C. Zhang, Y. Shen, Z. Zhou, J. Yu, Y. Li, W. Wei, S. Liu, Y. Zhang, J.
18450–18459. Mater. Chem. A 3 (2015) 5126–5131.
[319] W. Tian, Q. Shen, N. Li, J. Zhou, RSC Adv. 6 (2016) 25568–25576. [371] X.D. Sun, Y.Y. Li, J. Zhou, C.H. Ma, Y. Wang, J.H. Zhu, J. Colloid Interface Sci.
[320] F. Raziq, Y. Qu, X. Zhang, M. Humayun, J. Wu, A. Zada, H. Yu, X. Sun, L. Jingo, J. 451 (2015) 108–116.
Phys. Chem. C 120 (2016) 98–107. [372] Q. Liang, Z. Li, X. Yu, Z.-H. Huang, F. Kang, Q.-H. Yang, Adv. Mater. 27 (2015)
[321] Z.-F. Huang, J. Song, L. Pan, Z. Wang, X. Zhang, J.-J. Zou, W. Mi, X. Zhang, L. 4634–4639.
Wang, Nano Energy 12 (2015) 646–656. [373] Z. Lin, X. Wang, ChemSusChem 7 (2014) 1547–1550.
[322] X. Ma, Y. Lv, J. Xu, Y. Liu, R. Zhang, Y. Zhu, J. Phys. Chem. C 116 (2012) [374] Y. Wang, X. Wang, M. Antonietti, Y. Zhang, ChemSusChem 3 (2010) 435–439.
23485–23493. [375] H. Yan, Chem. Commun. 48 (2012) 3430–3432.
[323] S. Hu, L. Ma, J. You, F. Li, Z. Fan, F. Wang, D. Liu, J. Gui, RSC Adv. 4 (2014) [376] W. Shen, L. Ren, H. Zhou, S. Zhang, W. Fan, J. Mater. Chem. 21 (2011)
21657–21663. 3890–3894.
[324] Y. Zhou, L. Zhang, J. Liu, X. Fan, B. Wang, M. Wang, W. Ren, J. Wang, M. Li, J. [377] Q. Fan, J. Liu, Y. Yu, S. Zuo, RSC Adv. 4 (2014) 61877–61883.
Shi, J. Mater. Chem. A 3 (2015) 3862–3867. [378] M. Zhang, J. Xu, R. Zong, Y. Zhu, Appl. Catal. B: Environ. 147 (2014) 229–235.
[325] D.-H. Lan, H.-T. Wang, L. Chen, C.-T. Au, S.-F. Yin, Carbon 100 (2016) 81–89. [379] J. Xu, Y. Wang, Y. Zhu, Langmuir 29 (2013) 10566–10572.
[326] J. Ran, T.Y. Ma, G. Gao, X.-W. Du, S.Z. Qiao, Energy Environ. Sci. 8 (2015) [380] Y. Zhang, J. Liu, G. Wu, W. Chen, Nanoscale 4 (2012) 5300–5303.
3708–3717. [381] F. He, G. Chen, Y. Yu, Y. Zhou, Y. Zheng, S. Hao, Chem. Commun. 51 (2015)
[327] Y. Wang, H.R. Li, J. Yao, X.C. Wang, M. Antonietti, Chem. Sci. 2 (2011) 425–427.
446–450. [382] F. He, G. Chen, Y. Zhou, Y. Yu, Y. Zheng, S. Hao, Chem. Commun. 51 (2015)
[328] L. Zhenzhen, W. Xinchen, Angew. Chem. Int. Ed. 52 (2013) 1735–1738. 16244–16246.
[329] C. Xu, Q. Han, Y. Zhao, L. Wang, Y. Li, L. Qu, J. Mater. Chem. A 3 (2015) [383] Z. Wang, W. Guan, Y. Sun, F. Dong, Y. Zhou, W.-K. Ho, Nanoscale 7 (2015)
1841–1846. 2471–2479.
[330] S.C. Yan, Z.S. Li, Z.G. Zou, Langmuir 26 (2010) 3894–3901. [384] J. Liu, M. Antonietti, Energy Environ. Sci. 6 (2013) 1486–1493.
[331] Y. Wang, Y. Di, M. Antonietti, H. Li, X. Chen, X. Wang, Chem. Mater. 22 (2010) [385] Y.-S. Jun, J. Park, S.U. Lee, A. Thomas, W.H. Hong, G.D. Stucky, Angew. Chem.
5119–5121. Int. Ed. 52 (2013) 11083–11087.
[332] S. Hu, L. Ma, J. You, F. Li, Z. Fan, G. Lu, D. Liu, J. Gui, Appl. Surf. Sci. 311 (2014) [386] T. Jordan, N. Fechler, J. Xu, T.J.K. Brenner, M. Antonietti, M. Shalom,
164–171. ChemCatChem 7 (2015) 2826–2830.
[333] H. Ma, S. Zhao, S. Li, N. Liu, RSC Adv. 5 (2015) 79585–79592. [387] Y. Liao, S. Zhu, J. Ma, Z. Sun, C. Yin, C. Zhu, X. Lou, D. Zhang, ChemCatChem 6
[334] S. Hu, L. Ma, Y. Xie, F. Li, Z. Fan, F. Wang, Q. Wang, Y. Wang, X. Kang, G. Wu, (2014) 3419–3425.
Dalton Trans. 44 (2015) 20889–20897. [388] M. Shalom, M. Guttentag, C. Fettkenhauer, S. Inal, D. Neher, A. Llobet, M.
[335] H. Ma, Y. Li, S. Li, N. Liu, Appl. Surf. Sci. 357 (2015) 131–138. Antonietti, Chem. Mater. 26 (2014) 5812–5818.
[336] J. Zhao, L. Ma, H. Wang, Y. Zhao, J. Zhang, S. Hu, Appl. Surf. Sci. 332 (2015) [389] J. Xu, T.J.K. Brenner, Z. Chen, D. Neher, M. Antonietti, M. Shalom, ACS Appl.
625–630. Mater. Interfaces 6 (2014) 16481–16486.
[337] S. Zhang, J. Li, M. Zeng, J. Li, J. Xu, X. Wang, Chem. Eur. J. 20 (2014) [390] J. Yang, X. Wu, X. Li, Y. Liu, M. Gao, X. Liu, L. Kong, S. Yang, Appl. Phys. A 105
9805–9812. (2011) 161–166.
[338] X. Fan, L. Zhang, R. Cheng, M. Wang, M. Li, Y. Zhou, J. Shi, ACS Catal. 5 (2015) [391] G. Dong, L. Zhang, J. Mater. Chem. 22 (2012) 1160–1166.
5008–5015. [392] K.K. Han, C.C. Wang, Y.Y. Li, M.M. Wan, Y. Wang, J.H. Zhu, RSC Adv. 3 (2013)
[339] W. Ho, Z. Zhang, W. Lin, S. Huang, X. Zhang, X. Wang, Y. Huang, ACS Appl. 9465–9469.
Mater. Interfaces 7 (2015) 5497–5505. [393] B. Shen, Z. Hong, Y. Chen, B. Lin, B. Gao, Mater. Lett. 118 (2014) 208–211.
[340] D. Zheng, C. Pang, Y. Liu, X. Wang, Chem. Commun. 51 (2015) 9706–9709. [394] Q. Cai, J. Shen, Y. Feng, Q. Shen, H. Yang, J. Alloy Compd. 628 (2015) 372–378.
[341] X. Fan, L. Zhang, M. Wang, W. Huang, Y. Zhou, M. Li, R. Cheng, J. Shi, Appl. [395] J. Ding, Q. Liu, Z. Zhang, X. Liu, J. Zhao, S. Cheng, B. Zong, W.-L. Dai, Appl.
Catal. B: Environ. 182 (2016) 68–73. Catal. B: Environ. 165 (2015) 511–518.
[342] J. Zhang, M. Zhang, S. Lin, X. Fu, X. Wang, J. Catal. 310 (2014) 24–30. [396] Q. Han, B. Wang, J. Gao, Z. Cheng, Y. Zhao, Z. Zhang, L. Qu, ACS Nano 10
[343] S. Chu, Y. Wang, Y. Guo, J. Feng, C. Wang, W. Luo, X. Fan, Z. Zou, ACS Catal. 3 (2016) 2745–2751.
(2013) 912–919. [397] Q. Gu, Y. Liao, L. Yin, J. Long, X. Wang, C. Xue, Appl. Catal. B: Environ. 165
[344] M.J. Bojdys, N. Severin, J.P. Rabe, A.I. Cooper, A. Thomas, M. Antonietti, (2015) 503–510.
Macromol. Rapid Commun. 34 (2013) 850–854. [398] Y. Cui, Z. Ding, X. Fu, X. Wang, Angew. Chem. Int. Ed. 51 (2012) 11814–11818.
[345] K. Schwinghammer, S. Hug, M.B. Mesch, J. Senker, B.V. Lotsch, Energy [399] H.-J. Li, D.-J. Qian, M. Chen, ACS Appl. Mater. Interfaces 7 (2015)
Environ. Sci. 8 (2015) 3345–3353. 25162–25170.
[346] Y. Cui, G. Zhang, Z. Lin, X. Wang, Appl. Catal. B: Environ. 181 (2016) 413–419. [400] X. Bai, L. Wang, R. Zong, Y. Zhu, J. Phys. Chem. C 117 (2013) 9952–9961.
[347] P. Niu, L.-C. Yin, Y.-Q. Yang, G. Liu, H.-M. Cheng, Adv. Mater. 26 (2014) [401] J. Yu, W. Liu, H. Yu, Cryst. Growth Des. 8 (2008) 930–934.
8046–8052. [402] J. Yu, H. Guo, S.A. Davis, S. Mann, Adv. Funct. Mater. 16 (2006) 2035–2041.
[348] Y. Kang, Y. Yang, L.-C. Yin, X. Kang, G. Liu, H.-M. Cheng, Adv. Mater. 27 (2015) [403] J. Yu, S. Liu, H. Yu, J. Catal. 249 (2007) 59–66.
4572–4577. [404] Y. Jiaguo, Y. Huogen, G. Hongtao, L. Mei, S. Mann, Small 4 (2008) 87–91.
[349] X. Li, G. Hartley, A.J. Ward, P.A. Young, A.F. Masters, T. Maschmeyer, J. Phys. [405] H. Yu, F. Chen, F. Chen, X. Wang, Appl. Surf. Sci. 358 (2015) 385–392.
Chem. C 119 (2015) 14938–14946. [406] S. Liu, J. Yu, S. Mann, J. Phys. Chem. C 113 (2009) 10712–10717.
[350] Q. Liang, Z. Li, Z.-H. Huang, F. Kang, Q.-H. Yang, Adv. Funct. Mater. 25 (2015) [407] J. Yu, S. Liu, M. Zhou, J. Phys. Chem. C 112 (2008) 2050–2057.
6885–6892. [408] L. Qi, B. Cheng, J. Yu, W. Ho, J. Hazard. Mater. 301 (2016) 522–530.
[351] P. Yang, J. Zhao, W. Qiao, L. Li, Z. Zhu, Nanoscale 7 (2015) 18887–18890. [409] P. Niu, Y. Yang, J.C. Yu, G. Liu, H.-M. Cheng, Chem. Commun. 50 (2014)
[352] Q. Tay, P. Kanhere, C.F. Ng, S. Chen, S. Chakraborty, A.C.H. Huan, T.C. Sum, R. 10837–10840.
Ahuja, Z. Chen, Chem. Mater. 27 (2015) 4930–4933. [410] H. Zhang, L.-H. Guo, L. Zhao, B. Wan, Y. Yang, J. Phys. Chem. Lett. 6 (2015)
[353] H.-Z. Wu, L.-M. Liu, S.-J. Zhao, Appl. Surf. Sci. 358 (2015) 363–369. 958–963.
[354] Y. Shiraishi, Y. Kofuji, H. Sakamoto, S. Tanaka, S. Ichikawa, T. Hirai, ACS Catal. [411] S. Barman, M. Sadhukhan, J. Mater. Chem. 22 (2012) 21832–21837.
5 (2015) 3058–3066. [412] Y. Tang, Y. Su, N. Yang, L. Zhang, Y. Lv, Anal. Chem. 86 (2014) 4528–4535.
[355] Y. Cao, Z. Zhang, J. Long, J. Liang, H. Lin, H. Lin, X. Wang, J. Mater. Chem. A [413] W. Wang, J.C. Yu, Z. Shen, D.K.L. Chan, T. Gu, Chem. Commun. 50 (2014)
(2014). 10148–10150.
[356] T. Xia, Y. Zhang, J. Murowchick, X. Chen, Catal. Today 225 (2013) 2–9. [414] X. Wang, G. Sun, N. Li, P. Chen, Chem. Soc. Rev. 45 (2016) 2239–2262.
[357] Z. Yang, Y. Zhang, Z. Schnepp, J. Mater. Chem. A 3 (2015) 14081–14092. [415] P. Niu, L. Zhang, G. Liu, H.-M. Cheng, Adv. Funct. Mater. 22 (2012)
[358] S.-W. Bian, Z. Ma, W.-G. Song, J. Phys. Chem. C 113 (2009) 8668–8672. 4763–4770.
[359] X.-H. Li, J. Zhang, X. Chen, A. Fischer, A. Thomas, M. Antonietti, X. Wang, [416] S. Yang, Y. Gong, J. Zhang, L. Zhan, L. Ma, Z. Fang, R. Vajtai, X. Wang, P.M.
Chem. Mater. 23 (2011) 4344–4348. Ajayan, Adv. Mater. 25 (2013) 2452–2456.
[360] J. Zhang, F. Guo, X. Wang, Adv. Funct. Mater. 23 (2013) 3008–3014. [417] F. Deng, X. Lu, L. Zhao, Y. Luo, X. Pei, X. Luo, S. Luo, J. Mater. Sci. 51 (2016)
[361] Y. Fukasawa, K. Takanabe, A. Shimojima, M. Antonietti, K. Domen, T. Okubo, 6998–7007.
Chem. Asian J. 6 (2011) 103–109. [418] J. Ma, X. Tan, T. Yu, X. Li, Int. J. Hydrogen Energy 41 (2016) 3877–3887.
[362] X.-H. Li, X. Wang, M. Antonietti, Chem. Sci. 3 (2012) 2170–2174. [419] Z. Zhang, K. Liu, Z. Feng, Y. Bao, B. Dong, Sci. Rep. U. K. 6 (2016).
[363] Y. Cui, J. Huang, X. Fu, X. Wang, Catal. Sci. Technol. 2 (2012) 1396–1402. [420] J. Tian, Q. Liu, C. Ge, Z. Xing, A.M. Asiri, A.O. Al-Youbi, X. Sun, Nanoscale 5
[364] J. Sun, J. Zhang, M. Zhang, M. Antonietti, X. Fu, X. Wang, Nat. Commun. 3 (2013) 8921–8924.
(2012) 1139.
118 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

[421] J. Tian, Q. Liu, A.M. Asiri, A.O. Al-Youbi, X. Sun, Anal. Chem. 85 (2013) [465] J.N. Coleman, M. Lotya, A. O’Neill, S.D. Bergin, P.J. King, U. Khan, K. Young, A.
5595–5599. Gaucher, S. De, R.J. Smith, I.V. Shvets, S.K. Arora, G. Stanton, H.-Y. Kim, K. Lee,
[422] N. Cheng, J. Tian, Q. Liu, C. Ge, A.H. Qusti, A.M. Asiri, A.O. Al-Youbi, X. Sun, G.T. Kim, G.S. Duesberg, T. Hallam, J.J. Boland, J.J. Wang, J.F. Donegan, J.C.
ACS Appl. Mater. Interfaces 5 (2013) 6815–6819. Grunlan, G. Moriarty, A. Shmeliov, R.J. Nicholls, J.M. Perkins, E.M. Grieveson,
[423] W. Ma, D. Han, M. Zhou, H. Sun, L. Wang, X. Dong, L. Niu, Chem. Sci. 5 (2014) K. Theuwissen, D.W. McComb, P.D. Nellist, V. Nicolosi, Science 331 (2011)
3946–3951. 568–571.
[424] Q. Lin, L. Li, S. Liang, M. Liu, J. Bi, L. Wu, Appl. Catal. B: Environ. 163 (2015) [466] D. Voiry, H. Yamaguchi, J. Li, R. Silva, D.C.B. Alves, T. Fujita, M. Chen, T. Asefa,
135–142. V.B. Shenoy, G. Eda, M. Chhowalla, Nat. Mater. 12 (2013) 850–855.
[425] J. Hong, S. Yin, Y. Pan, J. Han, T. Zhou, R. Xu, Nanoscale 6 (2014) [467] F. Song, X. Hu, Nat. Commun. 5 (2014) 4477.
14984–14990. [468] T. Ndlovu, A.T. Kuvarega, O.A. Arotiba, S. Sampath, R.W. Krause, B.B. Mamba,
[426] X. She, H. Xu, Y. Xu, J. Yan, J. Xia, L. Xu, Y. Song, Y. Jiang, Q. Zhang, H. Li, J. Appl. Surf. Sci. 300 (2014) 159–164.
Mater. Chem. A 2 (2014) 2563–2570. [469] V.Z. Baldissarelli, T. de Souza, L. Andrade, H.J. Cappa de Oliveira, R.d.F.
[427] S. Bai, X. Wang, C. Hu, M. Xie, J. Jiang, Y. Xiong, Chem. Commun. 50 (2014) Peralta Muniz Moreira, Appl. Surf. Sci. 359 (2015) 868–874.
6094–6097. [470] F. Cheng, H. Wang, X. Dong, Chem. Commun. 51 (2015) 7176–7179.
[428] L. Ma, H. Fan, M. Li, H. Tian, J. Fang, G. Dong, J. Mater. Chem. A 3 (2015) [471] G. Liu, P. Niu, C. Sun, S.C. Smith, Z. Chen, G.Q. Lu, H.-M. Cheng, J. Am. Chem.
22404–22412. Soc. 132 (2010) 11642–11648.
[429] M. Ayan-Varela, S. Villar-Rodil, J.I. Paredes, J.M. Munuera, A. Pagan, A.A. [472] P. Niu, G. Liu, H.-M. Cheng, J. Phys. Chem. C 116 (2012) 11013–11018.
Lozano-Perez, J.L. Cenis, A. Martinez-Aonso, J.M.D. Tascon, ACS Appl. Mater. [473] Y. Wang, J. Hong, W. Zhang, R. Xu, Catal. Sci. Technol. 3 (2013) 1703–1711.
Interfaces 7 (2015) 24032–24045. [474] D.J. Martin, K. Qiu, S.A. Shevlin, A.D. Handoko, X. Chen, Z. Guo, J. Tang,
[430] Y. Yin, J. Han, X. Zhang, Y. Zhang, J. Zhou, D. Muir, R. Sutarto, Z. Zhang, S. Liu, Angew. Chem. Int. Ed. 53 (2014) 9240–9245.
B. Song, RSC Adv. 4 (2014) 32690–32697. [475] V.W.-h. Lau, M.B. Mesch, V. Duppel, V. Blum, J. Senker, B.V. Lotsch, J. Am.
[431] L. Ma, H. Fan, J. Wang, Y. Zhao, H. Tian, G. Dong, Appl. Catal. B: Environ. 190 Chem. Soc. 137 (2014) 1064–1072.
(2016) 93–102. [476] J. Low, S. Cao, J. Yu, S. Wageh, Chem. Commun. 50 (2014) 10768–10777.
[432] J. Tong, L. Zhang, F. Li, K. Wang, L. Han, S. Cao, RSC Adv. 5 (2015) [477] J. Zhang, X. Wang, Angew. Chem. Int. Ed. 54 (2015) 7230–7232.
88149–88153. [478] E. Cheng, W. Yin, S. Bai, R. Qiao, Y. Zhong, Z. Li, Mater. Lett. 146 (2015) 87–90.
[433] S. Zhang, J. Li, X. Wang, Y. Huang, M. Zeng, J. Xu, ACS Appl. Mater. Interfaces [479] X. Wei, C. Shao, X. Li, N. Lu, K. Wang, Z. Zhang, Y. Liu, Nanoscale 8 (2016)
6 (2014) 22116–22125. 11034–11043.
[434] Y. Ma, E. Liu, X. Hu, C. Tang, J. Wan, J. Li, J. Fan, Appl. Surf. Sci. 358 (2015) [480] S. Tonda, S. Kumar, V. Shanker, Mater. Res. Bull. 75 (2016) 51–58.
246–251. [481] J. Xue, S. Ma, Y. Zhou, Z. Zhang, M. He, ACS Appl. Mater. Interfaces 7 (2015)
[435] F. Dong, Y. Li, Z. Wang, W.-K. Ho, Appl. Surf. Sci. 358 (2015) 393–403. 9630–9637.
[436] F. Chang, J. Zhang, Y. Xie, J. Chen, C. Li, J. Wang, J. Luo, B. Deng, X. Hu, Appl. [482] J. Xue, S. Ma, Y. Zhou, Q. Wang, RSC Adv. 5 (2015) 88249–88257.
Surf. Sci. 311 (2014) 574–581. [483] K. Dai, J. Lv, L. Lu, C. Liang, L. Geng, G. Zhu, Mater. Chem. Phys. 177 (2016)
[437] Q. Gu, Z. Gao, H. Zhao, Z. Lou, Y. Liao, C. Xue, RSC Adv. 5 (2015) 49317–49325. 529–537.
[438] Y. Li, R. Jin, X. Fang, Y. Yang, M. Yang, X. Liu, Y. Xing, S. Song, J. Hazard. Mater. [484] D. Chen, Z. Wang, Y. Du, G. Yang, T. Ren, H. Ding, Catal. Today 258 (2015)
313 (2016) 219–228. 41–48.
[439] F. Chang, Y. Xie, J. Zhang, J. Chen, C. Li, J. Wang, J. Luo, B. Deng, X. Hu, Rsc. [485] T. Zhou, Y. Xu, H. Xu, H. Wang, Z. Da, S. Huang, H. Ji, H. Li, Ceram. Int. 40
Adv. 4 (2014) 28519–28528. (2014) 9293–9301.
[440] S. Deng, P. Yuan, X. Ji, D. Shan, X. Zhang, ACS Appl. Mater. Interfaces 7 (2015) [486] Y. Yang, W. Guo, Y. Guo, Y. Zhao, X. Yuan, Y. Guo, J. Hazard. Mater. 271
543–552. (2014) 150–159.
[441] L. Huang, Y. Li, H. Xu, Y. Xu, J. Xia, K. Wang, H. Li, X. Cheng, RSC Adv. 3 (2013) [487] Y. Li, Y. Zhao, L. Fang, R. Jin, Y. Yang, Y. Xing, Mater. Lett. 126 (2014) 5–8.
22269–22279. [488] X. Bai, R. Zong, C. Li, D. Liu, Y. Liu, Y. Zhu, Appl. Catal. B: Environ. 147 (2014)
[442] P. Qiu, H. Chen, C. Xu, N. Zhou, F. Jiang, X. Wang, Y. Fu, J. Mater. Chem. A 3 82–91.
(2015) 24237–24244. [489] Y. Yang, Y. Guo, F. Liu, X. Yuan, Y. Guo, S. Zhang, W. Guo, M. Huo, Appl. Catal.
[443] X. Lu, K. Xu, P. Chen, K. Jia, S. Liu, C. Wu, J. Mater. Chem. A 2 (2014) B: Environ. 142 (2013) 828–837.
18924–18928. [490] Y.-S. Xu, W.-D. Zhang, ChemCatChem 5 (2013) 2343–2351.
[444] G. Liu, T. Wang, H. Zhang, X. Meng, D. Hao, K. Chang, P. Li, T. Kako, J. Ye, [491] Y. Xu, H. Xu, J. Yan, H. Li, L. Huang, J. Xia, S. Yin, H. Shu, Colloid Surf. A 436
Angew. Chem. Int. Ed. 54 (2015) 13561–13565. (2013) 474–483.
[445] M. Wu, J.-M. Yan, X.-N. Tang, M. Zhao, Q. Jiang, ChemSusChem 7 (2014) [493] L.G. Devi, R. Kavitha, Appl. Surf. Sci. 360 (2016) 601–622.
2654–2658. [494] N.E. Motl, E. Ewusi-Annan, I.T. Sines, L. Jensen, R.E. Schaak, J. Phys. Chem. C
[446] N. Cheng, P. Jiang, Q. Liu, J. Tian, A.M. Asiri, X. Sun, Analyst 139 (2014) 114 (2010) 19263–19269.
5065–5068. [495] K.K.M., B.K., N.G., S.B., V.A., Appl. Catal. B: Environ. 199 (2016) 282–291.
[447] Z. Huang, F. Li, B. Chen, G. Yuan, RSC Adv. 5 (2015) 14027–14033. [496] E. Liu, L. Qi, J. Bian, Y. Chen, X. Hu, J. Fan, H. Liu, C. Zhu, Q. Wang, Mater. Res.
[448] Z. Huang, F. Li, B. Chen, G. Yuan, Catal. Sci. Technol. 4 (2014) 4258–4264. Bull. 68 (2015) 203–209.
[449] H. Xu, J. Yan, X. She, L. Xu, J. Xia, Y. Xu, Y. Song, L. Huang, H. Li, Nanoscale 6 [497] J.A. Jiménez, J. Alloy Compd. 656 (2016) 685–688.
(2014) 1406–1415. [498] Y. Cheng, Y. Lin, J. Xu, J. He, T. Wang, G. Yu, D. Shao, W.-H. Wang, F. Lu, L. Li,
[450] H. Zhao, H. Yu, X. Quan, S. Chen, Y. Zhang, H. Zhao, H. Wang, Appl. Catal. B: X. Du, W. Wang, H. Liu, R. Zheng, Appl. Surf. Sci. 366 (2016) 120–128.
Environ. 152 (2014) 46–50. [499] S. Yu, H. Huang, F. Dong, M. Li, N. Tian, T. Zhang, Y. Zhane, ACS Appl. Mater.
[451] H. Zhao, H. Yu, X. Quan, S. Chen, H. Zhao, H. Wang, RSC Adv. 4 (2014) Interfaces 7 (2015) 27925–27933.
624–628. [500] Y. Sun, Z. Zhao, F. Dong, W. Zhang, Phys. Chem. Chem. Phys. 17 (2015)
[452] X. Dang, X. Zhang, W. Zhang, X. Dong, G. Wang, C. Ma, X. Zhang, H. Ma, M. 10383–10390.
Xue, RSC Adv. 5 (2015) 15052–15058. [501] F. Dong, Q. Li, Y. Sun, W.-K. Ho, ACS Catal. 4 (2014) 4341–4350.
[453] H. Wang, Y. Su, H. Zhao, H. Yu, S. Chen, Y. Zhang, X. Quan, Environ. Sci. [502] L. Ge, F. Zuo, J. Liu, Q. Ma, C. Wang, D. Sun, L. Bartels, P. Feng, J. Phys. Chem. C
Technol. 48 (2014) 11984–11990. 116 (2012) 13708–13714.
[454] X. She, L. Liu, H. Ji, Z. Mo, Y. Li, L. Huang, D. Du, H. Xu, H. Li, Appl. Catal. B: [503] S.-W. Cao, Y.-P. Yuan, J. Fang, M.M. Shahjamali, F.Y.C. Boey, J. Barber, S.C.J.
Environ. 187 (2016) 144–153. Loo, C. Xue, Int. J. Hydrogen Energy 38 (2013) 1258–1266.
[455] W. Zhao, Y. Guo, S. Wang, H. He, C. Sun, S. Yang, Appl. Catal. B: Environ. 165 [504] C.-z. Zheng, C.-y. Zhang, G.-h. Zhang, D.-j. Zhao, Y.-z. Wang, Mater. Res. Bull.
(2015) 335–343. 55 (2014) 212–215.
[456] J.H. Lee, M.J. Park, S.J. Yoo, J.H. Jang, H.-J. Kim, S.W. Nam, C.W. Yoon, J.Y. Kim, [505] W. Chen, T.-Y. Liu, T. Huang, X.-H. Liu, J.-W. Zhu, G.-R. Duan, X.-J. Yang, Appl.
Nanoscale 7 (2015) 10334–10339. Surf. Sci. 355 (2015) 379–387.
[457] X. Li, H. Ren, Z. Zou, J. Sun, J. Wang, Z. Liu, Chem. Commun. 52 (2016) [506] F. Jiang, T. Yan, H. Chen, A. Sun, C. Xu, X. Wang, Appl. Surf. Sci. 295 (2014)
453–456. 164–172.
[458] X. Guo, Y. Wang, F. Wu, Y. Ni, S. Kokot, Microchim. Acta 183 (2016) 773–780. [507] X. Dai, M. Xie, S. Meng, X. Fu, S. Chen, Appl. Catal. B: Environ. 158 (2014)
[459] J. Tong, L. Zhang, F. Li, M. Li, S. Cao, Phys. Chem. Chem. Phys. 17 (2015) 382–390.
23532–23537. [508] Y. Cui, Chin. J. Catal. 36 (2015) 372–379.
[460] X. Yuan, C. Zhou, Y. Jin, Q. Jing, Y. Yang, X. Shen, Q. Tang, Y. Mu, A.-K. Du, J. [509] K. Takanabe, K. Kamata, X. Wang, M. Antonietti, J. Kubota, K. Domen, Phys.
Colloid Interface Sci. 468 (2016) 211–219. Chem. Chem. Phys. 12 (2010) 13020–13025.
[461] K. Zhu, W. Wang, A. Meng, M. Zhao, J. Wang, M. Zhao, D. Zhang, Y. Jia, C. Xu, [510] X. Zhang, T. Peng, L. Yu, R. Li, Q. Li, Z. Li, ACS Catal. 5 (2015) 504–510.
Z. Li, RSC Adv. 5 (2015) 56239–56243. [511] L. Yu, X. Zhang, C. Zhuang, L. Lin, R. Li, T. Peng, Phys. Chem. Chem. Phys. 16
[462] Y. Yu, Q. Zhou, J. Wang, Chem. Commun. 52 (2016) 3396–3399. (2014) 4106–4114.
[463] V. Nicolosi, M. Chhowalla, M.G. Kanatzidis, M.S. Strano, J.N. Coleman, [512] X. Zhang, B. Peng, T. Peng, L. Yu, R. Li, J. Zhang, J. Power Sources 298 (2015)
Science 340 (2013) 1226419. 30–37.
[464] Y. Hernandez, V. Nicolosi, M. Lotya, F.M. Blighe, Z.Y. Sun, S. De, I.T. [513] H. Dai, S. Zhang, G. Xu, Y. Peng, L. Gong, X. Li, Y. Li, Y. Lin, G. Chen, RSC Adv. 4
McGovern, B. Holland, M. Byrne, Y.K. Gun’ko, J.J. Boland, P. Niraj, G. (2014) 58226–58230.
Duesberg, S. Krishnamurthy, R. Goodhue, J. Hutchison, V. Scardaci, A.C. [514] X. Zhang, L. Yu, C. Zhuang, T. Peng, R. Li, X. Li, ACS Catal. 4 (2014) 162–170.
Ferrari, J.N. Coleman, Nat. Nanotechnol. 3 (2008) 563–568. [515] X. Zhang, L. Yu, R. Li, T. Peng, X. Li, Catal. Sci. Technol. 4 (2014) 3251–3260.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 119

[516] H. Zhang, S. Li, R. Lu, A. Yu, ACS Appl. Mater. Interfaces 7 (2015) [573] W. Wang, H. Cheng, B. Huang, X. Liu, X. Qin, X. Zhang, Y. Dai, J. Colloid
21868–21874. Interface Sci. 442 (2015) 97–102.
[517] J. Xu, Y. Li, S. Peng, Int. J. Hydrogen Energy 40 (2015) 353–362. [574] Y. Yang, F. Zhou, S. Zhan, Y. Liu, Y. Yin, J. Inorg. Organomet. Polym. Mater. 26
[518] J. Xu, Y. Li, S. Peng, G. Lu, S. Li, Phys. Chem. Chem. Phys. 15 (2013) 7657–7665. (2016) 91–99.
[519] S. Min, G. Lu, J. Phys. Chem. C 116 (2012) 19644–19652. [575] S. Yin, J. Di, M. Li, Y. Sun, J. Xia, H. Xu, W. Fan, H. Li, J. Mater. Sci. 51 (2016)
[520] T. Jia, M.M.J. Li, L. Ye, S. Wiseman, G. Liu, J. Qu, K. Nakagawa, S.C.E. Tsang, 4769–4777.
Chem. Commun. 51 (2015) 13496–13499. [576] L. Ge, C. Han, J. Liu, Appl. Catal. B: Environ. 108 (2011) 100–107.
[521] Z. Li, Y. Wu, G. Lu, Appl. Catal. B: Environ. 188 (2016) 56–64. [577] L. Ge, C. Han, J. Liu, in: H.B. Ji, Y. Chen, S.Z. Chen (Eds.), Advanced Materials
[522] J. Qin, J. Huo, P. Zhang, J. Zeng, T. Wang, H. Zeng, Nanoscale 8 (2016) and Processes Ii, Pts 1–3, 2012, pp. 957–960.
2249–2259. [578] Y. Wang, X. Bai, C. Pan, J. He, Y. Zhu, J. Mater. Chem. 22 (2012) 11568–11573.
[523] J. Yu, S. Wang, J. Low, W. Xiao, Phys. Chem. Chem. Phys. 15 (2013) [579] M.-S. Gui, P.-F. Wang, D. Yuan, Y.-K. Yang, Chin. J. Inorg. Chem. 29 (2013)
16883–16890. 2057–2064.
[524] L. Liu, Y. Qi, J. Hu, Y. Liang, W. Cui, Appl. Surf. Sci. 351 (2015) 1146–1154. [580] H. Wang, J. Lu, F. Wang, W. Wei, Y. Chang, S. Dong, Ceram. Int. 40 (2014)
[525] J. Chen, S. Shen, P. Guo, M. Wang, P. Wu, X. Wang, L. Guo, Appl. Catal. B: 9077–9086.
Environ. 152 (2014) 335–341. [581] L. Liu, Y. Qi, J. Lu, S. Lin, W. An, J. Hu, Y. Liang, W. Cui, RSC Adv. 5 (2015)
[526] L. Liu, Y. Qi, J. Hu, W. An, S. Lin, Y. Liang, W. Cui, Mater. Lett. 158 (2015) 99339–99346.
278–281. [582] M. Wang, M.H. Fang, C. Tang, L.N. Zhang, Z.H. Huang, Y.G. Liu, X.W. Wu, J.
[527] Y. Wang, R. Shi, J. Lin, Y. Zhu, Energy Environ. Sci. 4 (2011) 2922–2929. Mater. Res. 31 (2016) 713–720.
[528] W. Liu, M. Wang, C. Xu, S. Chen, Chem. Eng. J. 209 (2012) 386–393. [583] S. Girish Kumar, K.S.R. Koteswara Rao, Appl. Surf. Sci. 355 (2015) 939–958.
[529] J.-X. Sun, Y.-P. Yuan, L.-G. Qiu, X. Jiang, A.-J. Xie, Y.-H. Shen, J.-F. Zhu, Dalton [584] J. Theerthagiri, R.A. Senthil, A. Priya, J. Madhavan, R.J.V. Michael, M.
Trans. 41 (2012) 6756–6763. Ashokkumar, RSC Adv. 4 (2014) 38222–38229.
[530] W. Liu, M. Wang, C. Xu, S. Chen, X. Fu, J. Mol. Catal. A: Chem. 368 (2013) 9–15. [585] D. Xiao, K. Dai, Y. Qu, Y. Yin, H. Chen, Appl. Surf. Sci. 358 (2015) 181–187.
[531] Y. Bu, Z. Chen, RSC Adv. 4 (2014) 45397–45406. [586] Y. Xu, S. Huang, M. Xie, Y. Li, H. Xu, L. Huang, Q. Zhang, H. Li, RSC Adv. 5
[532] D. Chen, K. Wang, T. Ren, H. Ding, Y. Zhu, Dalton Trans. 43 (2014) (2015) 95727–95735.
13105–13114. [587] K.C. Christoforidis, T. Montini, E. Bontempi, S. Zafeiratos, J.J. Delgado Jaen, P.
[533] D. Chen, K. Wang, D. Xiang, R. Zong, W. Yao, Y. Zhu, Appl. Catal. B: Environ. Fornasiero, Appl. Catal. B: Environ. 187 (2016) 171–180.
147 (2014) 554–561. [588] F. Dong, Z. Zhao, T. Xiong, Z. Ni, W. Zhang, Y. Sun, W.-K. Ho, ACS Appl. Mater.
[534] S. Kumar, A. Baruah, S. Tonda, B. Kumar, V. Shanker, B. Sreedhar, Nanoscale 6 Interfaces 5 (2013) 11392–11401.
(2014) 4830–4842. [589] X. Ding, Y. Li, J. Zhao, Y. Zhu, Y. Li, W. Deng, C. Wang, APL Mater. 3 (2015)
[535] A. Akhundi, A. Habibi-Yangjeh, Appl. Surf. Sci. 358 (2015) 261–269. 104410.
[536] Y. He, Y. Wang, L. Zhang, B. Teng, M. Fan, Appl. Catal. B: Environ. 168 (2015) [590] W. Li, C. Feng, S. Dai, J. Yue, F. Hua, H. Hou, Appl. Catal. B: Environ. 168
1–8. (2015) 465–471.
[537] W.-K. Jo, N.C.S. Selvam, J. Hazard. Mater. 299 (2015) 462–470. [591] D. Wang, Z. Xu, Q. Luo, X. Li, J. An, R. Yin, C. Bao, J. Mater. Sci. 51 (2016)
[538] L. Huang, H. Xu, Y. Li, H. Li, X. Cheng, J. Xia, Y. Xu, G. Cai, Dalton Trans. 42 893–902.
(2013) 8606–8616. [592] L. Zhang, F. Huang, C. Liang, L. Zhou, X. Zhang, Q. Pang, J. Taiwan Inst. Chem.
[539] K.-i. Katsumata, R. Motoyoshi, N. Matsushita, K. Okada, J. Hazard. Mater. 260 Eng. 60 (2016) 643–650.
(2013) 475–482. [593] P. Zhou, J. Yu, M. Jaroniec, Adv. Mater. 26 (2014) 4920–4935.
[540] Y. Zang, L. Li, Y. Zuo, H. Lin, G. Li, X. Guan, RSC Adv. 3 (2013) 13646–13650. [594] K. Maeda, ACS Catal. 3 (2013) 1486–1503.
[541] D. An Tran, T. Xuan Dieu Nguyen, N. Phi Hung, T. Viet Nga Nguyen, S.J. Kim, [595] Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhong, C. Wang, Z. Pan, T.
V. Vien, B. Korean, Chem. Soc. 35 (2014) 1794–1798. Takata, M. Nakabayashi, N. Shibata, Y. Li, I.D. Sharp, A. Kudo, T. Yamada, K.
[542] I. Aslam, C. Cao, M. Tanveer, W.S. Khan, M. Tahir, M. Abid, F. Idrees, F.K. Butt, Domen, Nat. Mater. 15 (2016) 611.
Z. Ali, N. Mahmood, New J. Chem. 38 (2014) 5462–5469. [596] L. Xiong, F. Yang, L. Yan, N. Yan, X. Yang, M. Qiu, Y. Yu, J. Phys. Chem. Solids
[543] M. Yang, S. Hu, F. Li, Z. Fan, F. Wang, D. Liu, J. Gui, Ceram. Int. 40 (2014) 72 (2011) 1104–1109.
11963–11969. [597] S. Hu, F. Zhou, L. Wang, J. Zhang, Catal. Commun. 12 (2011) 794–797.
[544] J. Zhao, Z. Ji, X. Shen, H. Zhou, L. Ma, Ceram. Int. 41 (2015) 5600–5606. [598] W.-K. Jo, T.S. Natarajan, Chem. Eng. J. 281 (2015) 549–565.
[545] C. Li, S. Wang, T. Wang, Y. Wei, P. Zhang, J. Gong, Small 10 (2014) 2783–2790. [599] W.-K. Jo, T. Adinaveen, J.J. Vijaya, N.C.S. Selvam, RSC Adv. 6 (2016)
[546] M. Ou, Q. Zhong, S. Zhang, J. Sol-Gel. Sci. Technol. 72 (2014) 443–454. 10487–10497.
[547] Y. Huang, M. Fu, T. He, Acta Phys. Chim. Sin. 31 (2015) 1145–1152. [600] J. Zhang, Y. Hu, X. Jiang, S. Chen, S. Meng, X. Fu, J. Hazard. Mater. 280 (2014)
[548] M. Ou, Q. Zhong, S. Zhang, L. Yu, J. Alloy Compd. 626 (2015) 401–409. 713–722.
[549] J. Zhang, F. Ren, M. Deng, Y. Wang, Phys. Chem. Chem. Phys. 17 (2015) [601] W. Yu, D. Xu, T. Peng, J. Mater. Chem. A 3 (2015) 19936–19947.
10218–10226. [602] Y. Liu, R. Wang, Z. Yang, H. Du, Y. Jiang, C. Shen, K. Liang, A. Xu, Chin. J. Catal.
[550] H.J. Kong, D.H. Won, J. Kim, S.I. Woo, Chem. Mater. 28 (2016) 1318–1324. 36 (2015) 2135–2144.
[551] G. Miao, D. Huang, X. Ren, X. Li, Z. Li, J. Xiao, Appl. Catal. B: Environ. 192 [603] N. Tian, H. Huang, Y. He, Y. Guo, T. Zhang, Y. Zhang, Dalton Trans. 44 (2015)
(2016) 72–79. 4297–4307.
[552] Z. Ni, Y. Sun, Y. Zhang, F. Dong, Appl. Surf. Sci. 365 (2016) 314–335. [604] J. Lv, K. Dai, J. Zhang, L. Geng, C. Liang, Q. Liu, G. Zhu, C. Chen, Appl. Surf. Sci.
[553] S. Kumar, T. Surendar, A. Baruah, V. Shanker, J. Mater. Chem. A 1 (2013) 358 (2015) 377–384.
5333–5340. [605] H. Katsumata, Y. Tachi, T. Suzuki, S. Kaneco, RSC Adv. 4 (2014) 21405–21409.
[554] F.-J. Zhang, F.-Z. Xie, S.-F. Zhu, J. Liu, J. Zhang, S.-F. Mei, W. Zhao, Chem. Eng. [606] S. Chen, Y. Hu, X. Jiang, S. Meng, X. Fu, Mater. Chem. Phys. 149 (2015)
J. 228 (2013) 435–441. 512–521.
[555] P. He, L. Song, S. Zhang, X. Wu, Q. Wei, Mater. Res. Bull. 51 (2014) 432–437. [607] H. Katsumata, T. Sakai, T. Suzuki, S. Kaneco, Ind. Eng. Chem. Res. 53 (2014)
[556] D. Jiang, J. Zhu, M. Chen, J. Xie, J. Colloid Interface Sci. 417 (2014) 115–120. 8018–8025.
[557] K. Shen, M.A. Gondal, R.G. Siddique, S. Shi, S. Wang, J. Sun, Q. Xu, Chin. J. [608] Y. He, L. Zhang, B. Teng, M. Fan, Environ. Sci. Technol. 49 (2015) 649–656.
Catal. 35 (2014) 78–84. [609] X. Chen, X. Huang, Z. Yi, Chem. Eur. J. 20 (2014) 17590–17596.
[558] S. Meng, X. Ning, T. Zhang, S.-F. Chen, X. Fu, Phys. Chem. Chem. Phys. 17 [610] Y. Bai, P.-Q. Wang, J.-Y. Liu, X.-J. Liu, RSC Adv. 4 (2014) 19456–19461.
(2015) 11577–11585. [611] F. Shi, L. Chen, M. Chen, D. Jiang, Chem. Commun. 51 (2015) 17144–17147.
[559] C. Tang, E. Liu, J. Fan, X. Hu, Y. Ma, J. Wan, RSC Adv. 5 (2015) 91979–91987. [612] X. Ma, Q. Jiang, W. Guo, M. Zheng, W. Xu, F. Ma, B. Hou, RSC Adv. 6 (2016)
[560] L. Liu, Y. Qi, J. Lu, S. Lin, W. An, Y. Liang, W. Cui, Appl. Catal. B: Environ. 183 28263–28269.
(2016) 133–141. [613] D. Ma, J. Wu, M. Gao, Y. Xin, T. Ma, Y. Sun, Chem. Eng. J. 290 (2016) 136–146.
[561] J. Fu, B. Chang, Y. Tian, F. Xi, X. Dong, J. Mater. Chem. A 1 (2013) 3083–3090. [614] J.-C. Wang, H.-C. Yao, Z.-Y. Fan, L. Zhang, J.-S. Wang, S.-Q. Zang, Z.-J. Li, ACS
[562] J. Zhang, Y. Wang, J. Jin, J. Zhang, Z. Lin, F. Huang, J. Yu, ACS Appl. Mater. Appl. Mater. Interfaces 8 (2016) 3765–3775.
Interfaces 5 (2013) 10317–10324. [615] X. Yang, Z. Chen, J. Xu, H. Tang, K. Chen, Y. Jiang, ACS Appl. Mater. Interfaces
[563] M. Lu, Z. Pei, S. Weng, W. Feng, Z. Fang, Z. Zheng, M. Huang, P. Liu, Phys. 7 (2015) 15285–15293.
Chem. Chem. Phys. 16 (2014) 21280–21288. [616] Y. Hong, Y. Jiang, C. Li, W. Fan, X. Yan, M. Yan, W. Shi, Appl. Catal. B: Environ.
[564] Z.L. Fang, H.F. Rong, Z.L. Ya, P. Qi, J. Mater. Sci. 50 (2015) 3057–3064. 180 (2016) 663–673.
[565] J. Liu, J. Phys. Chem. C 119 (2015) 28417–28423. [617] Y. He, L. Zhang, X. Wang, Y. Wu, H. Lin, L. Zhao, W. Weng, H. Wan, M. Fan,
[566] Y. Xu, W.-D. Zhang, Eur. J. Inorg. Chem 2015 (2015) 1744–1751. RSC Adv. 4 (2014) 13610–13619.
[567] S. Shi, M.A. Gondal, A.A. Al-Saadi, R. Fajgar, J. Kupcik, X. Chang, K. Shen, Q. [618] H. Cheng, J. Hou, O. Takeda, X.-M. Guo, H. Zhu, J. Mater. Chem. A 3 (2015)
Xu, Z.S. Seddigi, J. Colloid Interface Sci. 416 (2014) 212–219. 11006–11013.
[568] S. Shi, M.A. Gondal, S.G. Rashid, Q. Qi, A.A. Al- Saadi, Z.H. Yamani, Y. Sui, Q. [619] X. Yang, H. Tang, J. Xu, M. Antonietti, M. Shalom, ChemSusChem 8 (2015)
Xu, K. Shen, Colloid Surf. A 461 (2014) 202–211. 1350–1358.
[569] W. Zhang, Y. Sun, F. Dong, W. Zhang, S. Duan, Q. Zhang, Dalton Trans. 43 [620] T. Ohno, N. Murakami, T. Koyanagi, Y. Yang, J. CO2 Util. 6 (2014) 17–25.
(2014) 12026–12036. [621] A.S. Cherevan, P. Gebhardt, C.J. Shearer, M. Matsukawa, K. Domen, D. Eder,
[570] H. Gu, T. Zhou, G. Shi, Talanta 132 (2015) 871–876. Energy Environ. Sci. 7 (2014) 791–796.
[571] L. Lei, H. Jin, Q. Zhang, J. Xu, D. Gao, Z. Fu, Dalton Trans. 44 (2015) 795–803. [622] F.-X. Xiao, S.-F. Hung, H.B. Tao, J. Miao, H.B. Yang, B. Liu, Nanoscale 6 (2014)
[572] Q. Li, X. Zhao, J. Yang, C.-J. Jia, Z. Jin, W. Fan, Nanoscale 7 (2015) 14950–14961.
18971–18983.
120 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

[623] B. Weng, M.-Q. Yang, N. Zhang, Y.-J. Xu, J. Mater. Chem. A 2 (2014) [678] Z.-F. Huang, J. Song, K. Li, M. Tahir, Y.-T. Wang, L. Pan, L. Wang, X. Zhang, J.-J.
9380–9389. Zou, J. Am. Chem. Soc. 138 (2016) 1359–1365.
[624] D. Jena, K. Banerjee, G.H. Xing, Nat. Mater. 13 (2014) 1076–1078. [679] J. Dong, M. Wang, X. Li, L. Chen, Y. He, L. Sun, ChemSusChem 5 (2012)
[625] N. Zhang, M.Q. Yang, Z.R. Tang, Y.J. Xu, ACS Nano 8 (2014) 623–633. 2133–2138.
[626] C. Han, M.-Q. Yang, N. Zhang, Y.-J. Xu, J. Mater. Chem. A 2 (2014) [680] K. Li, F.-Y. Su, W.-D. Zhang, Appl. Surf. Sci. 375 (2016) 110–117.
19156–19166. [681] L. Ge, C. Han, Appl. Catal. B: Environ. 117 (2012) 268–274.
[627] S. Bai, J. Ge, L. Wang, M. Gong, M. Deng, Q. Kong, L. Song, J. Jiang, Q. Zhang, Y. [682] J. Zhang, F. Huang, Appl. Surf. Sci. 358 (2015) 287–295.
Luo, Y. Xie, Y. Xiong, Adv. Mater. 26 (2014) 5689. [683] F. He, G. Chen, Y. Zhou, Y. Yu, L. Li, S. Hao, B. Liu, J. Mater. Chem. A 4 (2016)
[628] L. Ge, C. Han, X. Xiao, L. Guo, Int. J. Hydrogen Energy 38 (2013) 6960–6969. 3822–3827.
[629] Q. Li, N. Zhang, Y. Yang, G. Wang, D.H.L. Ng, Langmuir 30 (2014) 8965–8972. [684] G. Zhang, S. Zang, L. Lin, Z.-A. Lan, G. Li, X. Wang, ACS Appl. Mater. Interfaces
[630] W.-c. Peng, X.-y. Li, Catal. Commun. 49 (2014) 63–67. 8 (2016) 2287–2296.
[631] Y. Tian, L. Ge, K. Wang, Y. Chai, Mater. Charact. 87 (2014) 70–73. [685] G. Zhang, S. Zang, X. Wang, ACS Catal. 5 (2014) 941–947.
[632] H. Zhao, Y. Dong, P. Jiang, H. Miao, G. Wang, J. Zhang, J. Mater. Chem. A 3 [686] S. Nayak, L. Mohapatra, K. Parida, J. Mater. Chem. A 3 (2015) 18622–18635.
(2015) 7375–7381. [687] Z. Guigang, H. Caijin, W. Xinchen, Small 11 (2015) 1215–1221.
[633] J. Li, E. Liu, Y. Ma, X. Hu, J. Wan, L. Sun, J. Fan, Appl. Surf. Sci. 364 (2016) [688] C. Han, L. Ge, C. Chen, Y. Li, X. Xiao, Y. Zhang, L. Guo, Appl. Catal. B: Environ.
694–702. 147 (2014) 546–553.
[634] M. Sun, Q. Yan, T. Yan, M. Li, D. Wei, Z. Wang, Q. Wei, B. Du, RSC Adv. 4 [689] J.S. Zhang, M. Grzelczak, Y.D. Hou, K. Maeda, K. Domen, X.Z. Fu, M.
(2014) 31019–31027. Antonietti, X.C. Wang, Chem. Sci. 3 (2012) 443–446.
[635] Z. Zhang, J. Huang, M. Zhang, Q. Yuan, B. Dong, Appl. Catal. B: Environ. 163 [690] L. Ge, C. Han, X. Xiao, L. Guo, Appl. Catal. B: Environ. 142 (2013) 414–422.
(2015) 298–305. [691] J. Yu, K. Wang, W. Xiao, B. Cheng, Phys. Chem. Chem. Phys. 16 (2014)
[636] Y. Liu, P. Chen, Y. Chen, H. Lu, J. Wang, Z. Yang, Z. Lu, M. Li, L. Fang, RSC Adv. 6 11492–11501.
(2016) 10802–10809. [692] W.-J. Ong, L.-L. Tan, S.-P. Chai, S.-T. Yong, Dalton Trans. 44 (2015)
[637] Y. Hou, Y. Zhu, Y. Xu, X. Wang, Appl. Catal. B: Environ. 156 (2014) 122–127. 1249–1257.
[638] M.S. Akple, J. Low, S. Wageh, A.A. Al-Ghamdi, J. Yu, J. Zhang, Appl. Surf. Sci. [693] H. Shi, C. Zhang, C. Zhou, G. Chen, RSC Adv. 5 (2015) 93615–93622.
358 (2015) 196–203. [694] G. Gao, Y. Jiao, E.R. Waclawik, A. Du, J. Am. Chem. Soc. 138 (2016) 6292–6297.
[639] S. Hu, W. Zhang, J. Bai, G. Lu, L. Zhang, G. Wu, RSC Adv. 6 (2016) [695] R. Kuriki, K. Sekizawa, O. Ishitani, K. Maeda, Angew. Chem. Int. Ed. 54 (2015)
25695–25702. 2406–2409.
[640] Z. Zhang, D. Jiang, D. Li, M. He, M. Chen, Appl. Catal. B: Environ. 183 (2016) [696] R. Kuriki, O. Ishitani, K. Maeda, Acs Appl. Mater. Interfaces 8 (2016)
113–123. 6011–6018.
[641] L. Ye, J. Liu, Z. Jiang, T. Peng, L. Zan, Appl. Catal. B: Environ. 142 (2013) 1–7. [697] K. Maeda, R. Kuriki, O. Ishitani, Chem. Lett. 45 (2016) 182–184.
[642] J. Hong, W. Zhang, Y. Wang, T. Zhou, R. Xu, ChemCatChem 6 (2014) [698] G. Zhang, Z.-A. Lan, X. Wang, ChemCatChem 7 (2015) 1422–1423.
2315–2321. [699] K. Maeda, K. Sekizawa, O. Ishitani, Chem. Commun. 49 (2013) 10127–10129.
[643] L. Zhang, M. Ou, H. Yao, Z. Li, D. Qu, F. Liu, J. Wang, J. Wang, Z. Li, Electrochim. [700] R. Kuriki, H. Matsunaga, T. Nakashima, K. Wada, A. Yamakata, O. Ishitani, K.
Acta 186 (2015) 292–301. Maeda, J. Am. Chem. Soc. 138 (2016) 5159–5170.
[644] N. Tian, Y. Zhang, C. Liu, S. Yu, M. Li, H. Huang, RSC Adv. 6 (2016) [701] L. Ye, D. Wu, K.H. Chu, B. Wang, H. Xie, H.Y. Yip, P.K. Wong, Chem. Eng. J.
10895–10903. (2016).
[645] Q. Zhang, H. Wang, S. Hu, G. Lu, J. Bai, X. Kang, D. Liu, J. Gui, RSC Adv. 5 [702] W.-J. Ong, L.-L. Tan, S.-P. Chai, S.-T. Yong, Chem. Commun. 51 (2015)
(2015) 42736–42743. 858–861.
[646] Q. Xiang, J. Yu, M. Jaroniec, J. Am. Chem. Soc. 134 (2012) 6575–6578. [703] H. Li, S. Gan, H. Wang, D. Han, L. Niu, Adv. Mater. 27 (2015) 6906–6913.
[647] W.K. Ho, J.C. Yu, J. Lin, J.G. Yu, P.S. Li, Langmuir 20 (2004) 5865–5869. [704] J. Yu, J. Jin, B. Cheng, M. Jaroniec, J. Mater. Chem. A 2 (2014) 3407–3416.
[648] Y. Lu, D. Wang, P. Yang, Y. Du, C. Lu, Catal. Sci. Technol. 4 (2014) 2650–2657. [705] Y. Wang, X. Bai, H. Qin, F. Wang, Y. Li, X. Li, S. Kang, Y. Zuo, L. Cui, ACS Appl.
[649] S. Bai, L. Wang, X. Chen, J. Du, Y. Xiong, Nano Res. 8 (2015) 175–183. Mater. Interfaces 8 (2016) 17212–17219.
[650] Y. Hou, Z. Wen, S. Cui, X. Guo, J. Chen, Adv. Mater. 25 (2013) 6291–6297. [706] X. Lu, T.H. Tan, Y.H. Ng, R. Amal, Chem. Eur. J. (2016), [Link]
[651] X. Hao, Z. Jin, S. Min, G. Lu, RSC Adv. 6 (2016) 23709–23717. 1002/chem.201601674.
[652] D. Lu, G. Zhang, Z. Wan, Appl. Surf. Sci. 358 (2015) 223–230. [707] M. Seredych, S. Los, D.A. Giannakoudakis, E. Rodriguez-Castellon, T.J.
[653] Z.a. Huang, Q. Sun, K. Lv, Z. Zhang, M. Li, B. Li, Appl. Catal. B: Environ. 164 Bandosz, ChemSusChem 9 (2016) 795–799.
(2015) 420–427. [708] L. Shi, T. Wang, H. Zhang, K. Chang, J. Ye, Adv. Funct. Mater. 25 (2015)
[654] L. Gu, J. Wang, Z. Zou, X. Han, J. Hazard. Mater. 268 (2014) 216–223. 5360–5367.
[655] K. Dai, L. Lu, C. Liang, Q. Liu, G. Zhu, Appl. Catal. B: Environ. 156 (2014) [709] S. Wang, J. Lin, X. Wang, Phys. Chem. Chem. Phys. 16 (2014) 14656–14660.
331–340. [710] X. Lu, J. Shen, J. Wang, Z. Cui, J. Xie, RSC Adv. 5 (2015) 15993–15999.
[656] C.P. Sajan, S. Wageh, A.A. Al- Ghamdi, J. Yu, S. Cao, Nano Res. 9 (2016) 3–27. [711] O. Fontelles-Carceller, M.J. Munoz-Batista, M. Fernandez-Garcia, A. Kubacka,
[657] C. Wang, X. Zhang, Y. Liu, Appl. Surf. Sci. 358 (2015) 28–45. ACS Appl. Mater. Interfaces 8 (2016) 2617–2627.
[658] J. Low, B. Cheng, J. Yu, M. Jaroniec, Energy Storage Mater. 3 (2016) 24–35. [712] Y. Fu, T. Huang, L. Zhang, J. Zhu, X. Wang, Nanoscale 7 (2015) 13723–13733.
[659] G. Li, X. Nie, J. Chen, Q. Jiang, T. An, P.K. Wong, H. Zhang, H. Zhao, H. [713] C. Min, C. Shen, R. Li, Y. Li, J. Qin, X. Yang, Ceram. Int. 42 (2016) 5575–5581.
Yamashita, Water. Res. 86 (2015) 17–24. [714] M. Zang, L. Shi, L. Liang, D. Li, J. Sun, RSC Adv. 5 (2015) 56136–56144.
[660] W. Wang, J.C. Yu, D. Xia, P.K. Wong, Y. Li, Environ. Sci. Technol. 47 (2013) [715] J. Xue, S. Ma, Y. Zhou, Z. Zhang, X. Liu, RSC Adv. 5 (2015) 58738–58745.
8724–8732. [716] Z.W. Tong, D. Yang, Y.Y. Sun, Z.Y. Jiang, RSC Adv. 5 (2015) 56913–56921.
[661] S. Xie, Q. Zhang, G. Liu, Y. Wang, Chem. Commun. 52 (2016) 35–59. [717] K. Tian, W.-J. Liu, H. Jiang, ACS Sustain. Chem. Eng. 3 (2015) 269–276.
[662] L. Yang, H. Zhou, T. Fan, D. Zhang, Phys. Chem. Chem. Phys. 16 (2014) [718] Y. Su, Y. Zhao, Y. Zhao, J. Lang, X. Xin, X. Wang, Appl. Surf. Sci. 358 (2015)
6810–6826. 213–222.
[663] F. Fina, H. Menard, J.T.S. Irvine, Phys. Chem. Chem. Phys. 17 (2015) [719] Z. Li, J. Wang, K. Zhu, F. Ma, A. Meng, Mater. Lett. 145 (2015) 167–170.
13929–13936. [720] X. Yao, X. Liu, X. Hu, ChemCatChem 6 (2014) 3409–3418.
[664] X. Li, W. Bi, L. Zhang, S. Tao, W. Chu, Q. Zhang, Y. Luo, C. Wu, Y. Xie, Adv. [721] Y. Bu, Z. Chen, W. Li, Appl. Catal. B: Environ. 144 (2014) 622–630.
Mater. 28 (2016) 2427–2431. [722] J. Cao, Y. Zhao, H. Lin, B. Xu, S. Chen, Mater. Res. Bull. 48 (2013) 3873–3880.
[665] D. Jiang, L. Chen, J. Xie, M. Chen, Dalton Trans. 43 (2014) 4878–4885. [723] L. Ge, C. Han, J. Liu, Y. Li, Appl. Catal. A: Gen. 409 (2011) 215–222.
[666] S. Samanta, S. Martha, K. Parida, ChemCatChem 6 (2014) 1453–1462. [724] H.-T. Ren, S.-Y. Jia, S.-H. Wu, T.-H. Zhang, X. Han, Mater. Lett. 142 (2015)
[667] J. Lang, M. Liu, Y. Su, L. Yan, X. Wang, Appl. Surf. Sci. 358 (2015) 252–260. 15–18.
[668] S. Liang, Y. Xia, S. Zhu, S. Zheng, Y. He, J. Bi, M. Liu, L. Wu, Appl. Surf. Sci. 358 [725] S. Ma, J. Xue, Y. Zhou, Z. Zhang, RSC Adv. 5 (2015) 40000–40006.
(2015) 304–312. [726] L. Shi, L. Liang, J. Ma, F. Wang, J. Sun, Catal. Sci. Technol. 4 (2014) 758–765.
[669] Z. Yan, Z. Sun, X. Liu, H. Jia, P. Du, Nanoscale 8 (2016) 4748–4756. [727] H.-T. Ren, S.-Y. Jia, Y. Wu, S.-H. Wu, T.-H. Zhang, X. Han, Ind. Eng. Chem. Res.
[670] Z. Chen, P. Sun, B. Fan, Z. Zhang, X. Fang, J. Phys. Chem. C 118 (2014) 53 (2014) 17645–17653.
7801–7807. [728] M. Xu, L. Han, S. Dong, ACS Appl. Mater. Interfaces 5 (2013) 12533–12540.
[671] Y. Lu, D. Chu, M. Zhu, Y. Du, P. Yang, Phys. Chem. Chem. Phys. 17 (2015) [729] C. Chang, Y. Fu, M. Hu, C. Wang, G. Shan, L. Zhu, Appl. Catal. B: Environ. 142
17355–17361. (2013) 553–560.
[672] Y.-N. Zhang, X.-H. Li, Y.-Y. Cai, L.-H. Gong, K.-X. Wang, J.-S. Chen, RSC Adv. 4 [730] Y. Li, X. Xu, P. Zhang, Y. Gong, H. Li, Y. Wang, RSC Adv. 3 (2013) 10973–10982.
(2014) 60873–60877. [731] Z. Zhang, M. Xu, W. Ho, X. Zhang, Z. Yang, X. Wang, Appl. Catal. B: Environ.
[673] L. Yin, Y.-P. Yuan, S.-W. Cao, Z. Zhang, C. Xue, RSC Adv. 4 (2014) 6127–6132. 184 (2016) 174–181.
[674] M. Fan, C. Song, T. Chen, X. Yan, D. Xu, W. Gu, W. Shi, L. Xiao, RSC Adv. 6 [732] S.K. Konda, M. Amiri, A. Chen, J. Phys. Chem. C 120 (2016) 14467–14473.
(2016) 34633–34640. [733] K. Sridharan, E. Jang, J.H. Park, J.-H. Kim, J.-H. Lee, T.J. Park, Chem. Eur. J. 21
[675] K. Mori, T. Itoh, H. Kakudo, T. Iwamoto, Y. Masui, M. Onaka, H. Yamashita, (2015) 9126–9132.
Phys. Chem. Chem. Phys. 17 (2015) 24086–24091. [734] H.-Y. Chen, L.-G. Qiu, J.-D. Xiao, S. Ye, X. Jiang, Y.-P. Yuan, RSC Adv. 4 (2014)
[676] A. Indra, P.W. Menezes, K. Kailasam, D. Hollmann, M. Schroeder, A. Thomas, 22491–22496.
A. Brueckner, M. Driess, Chem. Commun. 52 (2016) 104–107. [735] W.-K. Jo, J.Y. Lee, N.C.S. Selvam, Chem. Eng. J. 289 (2016) 306–318.
[677] S.-W. Cao, Y.-P. Yuan, J. Barber, S.C.J. Loo, C. Xue, Appl. Surf. Sci. 319 (2014) [736] J.-Y. Hu, K. Tian, H. Jiang, Chemosphere 148 (2016) 34–40.
344–349. [737] C. Li, F. Raziq, C. Liu, Z. Li, L. Sun, L. Jing, Appl. Surf. Sci. 358 (2015) 240–245.
[738] C. Liu, L. Jing, L. He, Y. Luan, C. Li, Chem. Commun. 50 (2014) 1999–2001.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 121

[739] Y. Min, X.F. Qi, Q. Xu, Y. Chen, CrystEngComm 16 (2014) 1287–1295. [793] M.Z. Rahman, J. Ran, Y. Tang, M. Jaroniec, S.Z. Qiao, J. Mater. Chem. A 4
[740] D. Xu, B. Cheng, S. Cao, J. Yu, Appl. Catal. B: Environ. 164 (2015) 380–388. (2016) 2445–2452.
[741] R.C. Pawar, V. Khare, C.S. Lee, Dalton Trans. 43 (2014) 12514–12527. [794] M. Wu, J.-M. Yan, X.-w. Zhang, M. Zhao, Appl. Surf. Sci. 354 (2015) 196–200.
[742] B. Yuan, J. Wei, T. Hu, H. Yao, Z. Jiang, Z. Fang, Z. Chu, Chin. J. Catal. 36 (2015) [795] Z. Huang, F. Li, B. Chen, G. Yuan, RSC Adv. 5 (2015) 102700–102706.
1009–1016. [796] L. Shi, L. Liang, F. Wang, M. Liu, K. Chen, K. Sun, N. Zhang, J. Sun, ACS Sustain.
[743] L. Wang, J. Ding, Y. Chai, Q. Liu, J. Ren, X. Liu, W.-L. Dai, Dalton Trans. 44 Chem. Eng. 3 (2015) 3412–3419.
(2015) 11223–11234. [797] Z. Jiang, D. Jiang, Z. Yan, D. Liu, K. Qian, J. Xie, Appl. Catal. B: Environ. 170
[744] M. Yan, F. Zhu, W. Gu, L. Sun, W. Shi, Y. Hua, RSC Adv. 6 (2016) 61162–61174. (2015) 195–205.
[745] S. Fang, Y. Xia, K. Lv, Q. Li, J. Sun, M. Li, Appl. Catal. B: Environ. 185 (2016) [798] Y. Zhou, L. Zhang, W. Huang, Q. Kong, X. Fan, M. Wang, J. Shi, Carbon 99
225–232. (2016) 111–117.
[746] X. Jian, X. Liu, H.-m. Yang, J.-g. Li, X.-l. Song, H.-y. Dai, Z.-h. Liang, Appl. Surf. [799] J. Fang, H. Fan, M. Li, C. Long, J. Mater. Chem. A 3 (2015) 13819–13826.
Sci. 370 (2016) 514–521. [800] Z.-A. Lan, G. Zhang, X. Wang, Appl. Catal. B: Environ. 192 (2016) 116–125.
[747] Y. Xu, H. Xu, L. Wang, J. Yan, H. Li, Y. Song, L. Huang, G. Cai, Dalton Trans. 42 [801] X. Wang, J. Chen, X. Guan, L. Guo, Int. J. Hydrogen Energy 40 (2015)
(2013) 7604–7613. 7546–7552.
[748] L. Pi, R. Jiang, W. Zhou, H. Zhu, W. Xiao, D. Wang, X. Mao, Appl. Surf. Sci. 358 [802] H. Liu, Z. Jin, Z. Xu, Dalton Trans. 44 (2015) 14368–14375.
(2015) 231–239. [803] H. Liu, Z. Xu, Z. Zhang, D. Ao, Appl. Catal. B: Environ. 192 (2016) 234–241.
[749] Q. Yu, X. Li, L. Zhang, X. Wang, Y. Tao, X. Wang, J. Polym. Mater. 32 (2015) [804] D. Zheng, G. Zhang, X. Wang, Appl. Catal. B: Environ. 179 (2015) 479–488.
411–422. [805] M. Li, L. Zhang, X. Fan, M. Wu, Y. Du, M. Wang, Q. Kong, L. Zhang, J. Shi, Appl.
[750] X.-H. Li, L.-G. Zhang, X.-X. Wang, Q.-B. Yu, Acta Phys. Chim. Sin. 31 (2015) Catal. B: Environ. 190 (2016) 36–43.
764–770. [806] F. Shi, L. Chen, C. Xing, D. Jiang, D. Li, M. Chen, RSC Adv. 4 (2014)
[751] X.-H. Li, L.-G. Zhang, X.-X. Wang, Q.-B. Yu, J. Inorg. Mater. 30 (2015) 62223–62229.
1018–1024. [807] D. Jiang, J. Li, C. Xing, Z. Zhang, S. Meng, M. Chen, ACS Appl. Mater. Interfaces
[752] B. Chai, X. Liao, F. Song, H. Zhou, Dalton Trans. 43 (2014) 982–989. 7 (2015) 19234–19242.
[753] X. Bai, L. Wang, Y. Wang, W. Yao, Y. Zhu, Appl. Catal. B: Environ. 152 (2014) [808] B. Li, Y. Wang, Y. Zeng, R. Wang, Mater. Lett. 178 (2016) 308–311.
262–270. [809] X. Zhou, Z. Luo, P. Tao, B. Jin, Z. Wu, Y. Huang, Mater. Chem. Phys. 143 (2014)
[754] S. Zhang, J. Li, X. Wang, Y. Huang, M. Zeng, J. Xu, J. Mater. Chem. A 3 (2015) 1462–1468.
10119–10126. [810] R. Cheng, X. Fan, M. Wang, M. Li, J. Tian, L. Zhang, RSC Adv. 6 (2016)
[755] R.C. Pawar, S. Kang, S.H. Ahn, C.S. Lee, RSC Adv. 5 (2015) 24281–24292. 18990–18995.
[756] L. Chen, H. Tao, T. Pang, J. Dong, X. Song, Chem. Lett. 44 (2015) 348–350. [811] R. Cheng, L. Zhang, X. Fan, M. Wang, M. Li, J. Shi, Carbon 101 (2016) 62–70.
[757] L. Shi, L. Liang, J. Ma, F. Wang, J. Sun, Dalton Trans. 43 (2014) 7236–7244. [812] J. Chen, S. Shen, P. Wu, L. Guo, Green Chem. 17 (2015) 509–517.
[758] X. Wang, K. Wang, K. Feng, F. Chen, H. Yu, J. Yu, J. Mol. Catal. A: Chem. 391 [813] M. Wu, J.-M. Yan, X.-W. Zhang, M. Zhao, Q. Jiang, J. Mater. Chem. A 3 (2015)
(2014) 92–98. 15710–15714.
[759] H. Yu, P. Xiao, P. Wang, J. Yu, Appl. Catal. B: Environ. 193 (2016) 217–225. [814] Z. Jiang, C. Zhu, W. Wan, K. Qian, J. Xie, J. Mater. Chem. A 4 (2016) 1806–1818.
[760] Y. Wang, F. Li, H. Li, L. Bai, L. Sun, Chem. Commun. 52 (2016) 3050–3053. [815] L. Chen, X. Zhou, B. Jin, J. Luo, X. Xu, L. Zhang, Y. Hong, Int. J. Hydrogen
[761] S. Ye, R. Chen, Y. Xu, F. Fan, P. Du, F. Zhang, X. Zong, T. Chen, Y. Qi, P. Chen, Z. Energy 41 (2016) 7292–7300.
Chen, C. Li, J. Catal. 338 (2016) 168–173. [816] R. Ye, H. Fang, Y.-Z. Zheng, N. Li, Y. Wang, X. Tao, ACS Appl. Mater. Interfaces
[762] D. Wang, R. Li, J. Zhu, J. Shi, J. Han, X. Zong, C. Li, J. Phys. Chem. C 116 (2012) 8 (2016) 13879–13889.
5082–5089. [817] W. Chen, T.-Y. Liu, T. Huang, X.-H. Liu, G.-R. Duan, X.-J. Yang, S.-M. Chen, RSC
[763] M.W. Kanan, D.G. Nocera, Science 321 (2008) 1072–1075. Adv. 5 (2015) 101214–101220.
[764] D. Wang, T. Hisatomi, T. Takata, C. Pan, M. Katayama, J. Kubota, K. Domen, [818] S. Pany, K.M. Parida, Phys. Chem. Chem. Phys. 17 (2015) 8070–8077.
Angew. Chem. Int. Ed. 52 (2013) 11252–11256. [819] C. Bo, P. Tianyou, M. Jing, L. Kan, Z. Ling, Phys. Chem. Chem. Phys. 14 (2012)
[765] K.R. Yoon, J.W. Ko, D.-Y. Youn, C.B. Park, I.-D. Kim, Green Chem. 18 (2016) 16745–16752.
944–950. [820] X. Yang, H. Huang, M. Kubota, Z. He, N. Kobayashi, X. Zhou, B. Jin, J. Luo,
[766] S. Hu, M.R. Shaner, J.A. Beardslee, M. Lichterman, B.S. Brunschwig, N.S. Mater. Res. Bull. 76 (2016) 79–84.
Lewis, Science 344 (2014) 1005–1009. [821] G. Zhao, X. Huang, F. Fina, G. Zhang, J.T.S. Irvine, Catal. Sci. Technol. 5 (2015)
[767] M.J. Kenney, M. Gong, Y. Li, J.Z. Wu, J. Feng, M. Lanza, H. Dai, Science 342 3416–3422.
(2013) 836–840. [822] K. Song, F. Xiao, L. Zhang, F. Yue, X. Liang, J. Wang, X. Su, J. Mol. Catal. A:
[768] Q. Yu, J. Xu, C. Wu, L. Guan, RSC Adv. 5 (2015) 65303–65307. Chem. 418 (2016) 95–102.
[769] G. Liao, S. Chen, X. Quan, H. Yu, H. Zhao, J. Mater. Chem. 22 (2012) [823] S. Cao, J. Jiang, b. zhu, J. Yu, Phys. Chem. Chem. Phys. 18 (2016) 19457–19463.
2721–2726. [824] D. Kong, J.J. Cha, H. Wang, H.R. Lee, Y. Cui, Energy Environ. Sci. 6 (2013)
[770] K. Dai, L. Lu, Q. Liu, G. Zhu, X. Wei, J. Bai, L. Xuan, H. Wang, Dalton Trans. 43 3553–3558.
(2014) 6295–6299. [825] Z. Zhao, H. Yang, J. Mol. Catal. A: Chem. 398 (2015) 268–274.
[771] X. Li, Y. Dai, Y. Ma, S. Han, B. Huang, Phys. Chem. Chem. Phys. 16 (2014) [826] D. Wang, Y. Zhang, W. Chen, Chem. Commun. 50 (2014) 1754–1756.
4230–4235. [827] X. Wang, G. Zhang, Z.-a. Lan, L. Lin, S. Lin, Chem. Sci. 7 (2016) 3062–3066.
[772] Y. Li, Y. Sun, F. Dong, W.-K. Ho, J. Colloid Interface Sci. 436 (2014) 29–36. [828] D.J. Martin, P.J.T. Reardon, S.J.A. Moniz, J. Tang, J. Am. Chem. Soc. 136 (2014)
[773] L. Xu, W.-Q. Huang, L.-L. Wang, Z.-A. Tian, W. Hu, Y. Ma, X. Wang, A. Pan, 12568–12571.
G.-F. Huang, Chem. Mater. 27 (2015) 1612–1621. [829] S.N. Frank, A.J. Bard, J. Am. Chem. Soc. 99 (1977) 303–304.
[774] J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz, S.-T. Lee, J. Zhong, [830] J. Yu, B. Wang, Appl. Catal. B: Environ. 94 (2010) 295–302.
Z. Kang, Science 347 (2015) 970–974. [831] J. Yu, G. Dai, B. Cheng, J. Phys. Chem. C 114 (2010) 19378–19385.
[775] Z. Ma, R. Sa, Q. Li, K. Wu, Phys. Chem. Chem. Phys. 18 (2016) 1050–1058. [832] J. Yu, G. Wang, B. Cheng, M. Zhou, Appl. Catal. B: Environ. 69 (2007) 171–180.
[776] G. Gao, Y. Jiao, F. Ma, Y. Jiao, E. Waclawik, A. Du, Phys. Chem. Chem. Phys. 17 [833] J. Yu, Y. Wang, W. Xiao, J. Mater. Chem. A 1 (2013) 10727–10735.
(2015) 31140–31144. [834] J. Yu, G. Dai, B. Huang, J. Phys. Chem. C 113 (2009) 16394–16401.
[777] Q. Liu, T. Chen, Y. Guo, Z. Zhang, X. Fang, Appl. Catal. B: Environ. 193 (2016) [835] J. Yu, G. Dai, Q. Xiang, M. Jaroniec, J. Mater. Chem. 21 (2011) 1049–1057.
248–258. [836] P. Madhusudan, J. Zhang, B. Cheng, J. Yu, Phys. Chem. Chem. Phys. 17 (2015)
[778] S. Hu, H. Wang, F. Wang, J. Bai, L. Zhang, X. Kang, G. Wu, B. Korean, Chem. 15339–15347.
Soc. 36 (2015) 2527–2533. [837] J. Yu, X. Yu, Environ. Sci. Technol. 42 (2008) 4902–4907.
[779] Z. Wu, H. Gao, S. Yan, Z. Zou, Dalton Trans. 43 (2014) 12013–12017. [838] Q. Xiang, J. Yu, M. Jaroniec, Phys. Chem. Chem. Phys. 13 (2011) 4853–4861.
[780] S. Patnaik, S. Martha, S. Acharya, K.M. Parida, Inorg. Chem. Front. 3 (2016) [839] G. Dai, J. Yu, G. Liu, J. Phys. Chem. C 115 (2011) 7339–7346.
336–347. [840] D. Chatterjee, S. Dasgupta, J. Photochem. Photobiol. C 6 (2005) 186–205.
[781] S. Cao, J. Yu, J. Photochem. Photobiol. C 27 (2016) 72–99. [841] L.-Y. Chen, W.-D. Zhang, Appl. Surf. Sci. 301 (2014) 428–435.
[782] R. Czerw, B. Foley, D. Tekleab, A. Rubio, P. Ajayan, D. Carroll, Phys. Rev. B 66 [842] B. Lin, C. Xue, X. Yan, G. Yang, G. Yang, B. Yang, Appl. Surf. Sci. 357 (2015)
(2002) 033408. 346–355.
[783] Q.J. Xiang, J.G. Yu, M. Jaroniec, Chem. Soc. Rev. 41 (2012) 782–796. [843] C.Q. Li, Z.M. Sun, Y.L. Xue, G.Y. Yao, S.L. Zheng, Adv. Powder Technol. 27
[784] Q. Xiang, J. Yu, J. Phys. Chem. Lett. 4 (2013) 753–759. (2016) 330–337.
[785] G. Xie, K. Zhang, B. Guo, Q. Liu, L. Fang, J.R. Gong, Adv. Mater. 25 (2013) [844] B. Korean, Chem. Soc. 36 (2015) 333–339.
3820–3839. [845] X. Chen, J. Wei, R. Hou, Y. Liang, Z. Xie, Y. Zhu, X. Zhang, H. Wang, Appl. Catal.
[786] F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini, A.C. Ferrari, R.S. Ruoff, B: Environ. 188 (2016) 342–350.
V. Pellegrini, Science 347 (2015) 1246501. [846] H. Wang, J. Li, C. Ma, Q. Guan, Z. Lu, P. Huo, Y. Yan, Appl. Surf. Sci. 329 (2015)
[787] Q. Xiang, B. Cheng, J. Yu, Angew. Chem. Int. Ed. 54 (2015) 11350–11366. 17–22.
[788] Y. Zhang, T. Mori, L. Niu, J. Ye, Energy Environ. Sci. 4 (2011) 4517–4521. [847] G. Li, X. Nie, Y. Gao, T. An, Appl. Catal. B: Environ. 180 (2016) 726–732.
[789] Y. Li, H. Zhang, P. Liu, D. Wang, Y. Li, H. Zhao, Small 9 (2013) 3336–3344. [848] Y. Chen, W. Huang, D. He, S. Yue, H. Huang, ACS Appl. Mater. Interfaces 6
[790] S.W. Hu, L.W. Yang, Y. Tian, X.L. Wei, J.W. Ding, J.X. Zhong, P.K. Chu, J. Colloid (2014) 14405–14414.
Interface Sci. 431 (2014) 42–49. [849] L. Shi, L. Liang, F. Wang, M. Liu, S. Zhong, J. Sun, Catal. Commun. 59 (2015)
[791] L.K. Putri, W.-J. Ong, W.S. Chang, S.-P. Chai, Appl. Surf. Sci. 358 (2015) 2–14. 131–135.
[792] G. Zhang, G. Li, X. Wang, ChemCatChem 7 (2015) 2864–2870. [850] H. Ji, F. Chang, X. Hu, W. Qin, J. Shen, Chem. Eng. J. 218 (2013) 183–190.
122 J. Wen et al. / Applied Surface Science 391 (2017) 72–123

[851] H. Zhang, L. Zhao, F. Geng, L.-H. Guo, B. Wan, Y. Yang, Appl. Catal. B: Environ. [902] Y. Liu, J. Wang, P. Yang, RSC Adv. 6 (2016) 34334–34341.
180 (2016) 656–662. [903] X. Wang, L. Zhang, H. Lin, Q. Nong, Y. Wu, T. Wu, Y. He, RSC Adv. 4 (2014)
[852] K. Li, Z. Zeng, L. Yana, S. Luo, X. Luo, M. Huo, Y. Guo, Appl. Catal. B: Environ. 40029–40035.
165 (2015) 428–437. [904] H. Xiao, W. Wang, G. Liu, Z. Chen, K. Lv, J. Zhu, Appl. Surf. Sci. 358 (2015)
[853] R.C. Pawar, Y. Pyo, S.H. Ahn, C.S. Lee, Appl. Catal. B: Environ. 176 (2015) 313–318.
654–666. [905] J. Cai, Y. He, X. Wang, L. Zhang, L. Dong, H. Lin, L. Zhao, X. Yi, W. Weng, H.
[854] S.P. Adhikari, H.R. Pant, H.J. Kim, C.H. Park, C.S. Kim, Ceram. Int. 41 (2015) Wan, RSC Adv. 3 (2013) 20862–20868.
12923–12929. [906] X. Rong, F. Qiu, J. Yan, H. Zhao, X. Zhu, D. Yang, RSC Adv. 5 (2015)
[855] Y. Li, J. Wang, Y. Yang, Y. Zhang, D. He, Q. An, G. Cao, J. Hazard. Mater. 292 24944–24952.
(2015) 79–89. [907] P. Liu, Y. Zhao, R. Qin, S. Mo, G. Chen, L. Gu, D.M. Chevrier, P. Zhang, Q. Guo,
[856] Q. Liu, C. Fan, H. Tang, X. Sun, J. Yang, X. Cheng, Appl. Surf. Sci. 358 (2015) D. Zang, B. Wu, G. Fu, N. Zheng, Science 352 (2016) 797–801.
188–195. [908] W. Bi, X. Li, L. Zhang, T. Jin, L. Zhang, Q. Zhang, Y. Luo, C. Wu, Y. Xie, Nat.
[857] Y. He, J. Cai, T. Li, Y. Wu, H. Lin, L. Zhao, M. Luo, Chem. Eng. J. 215 (2013) Commun. 6 (2015) 8647.
721–730. [909] H. Yu, G. Cao, F. Chen, X. Wang, J. Yu, M. Lei, Appl. Catal. B: Environ. 160
[858] T. Li, L. Zhao, Y. He, J. Cai, M. Luo, J. Lin, Appl. Catal. B: Environ. 129 (2013) (2014) 658–665.
255–263. [910] H. Yu, W. Chen, X. Wang, Y. Xu, J. Yu, Appl. Catal. B: Environ. 187 (2016)
[859] Y. Zang, L. Li, X. Li, R. Lin, G. Li, Chem. Eng. J. 246 (2014) 277–286. 163–170.
[860] L. Liu, Y. Qi, J. Yang, W. Cui, X. Li, Z. Zhang, Appl. Surf. Sci. 358 (2015) [911] H. Yu, L. Xu, P. Wang, X. Wang, J. Yu, Appl. Catal. B: Environ. 144 (2014)
319–327. 75–82.
[861] R.M. Mohamed, Ceram. Int. 41 (2015) 1197–1204. [912] H. Yu, X. Huang, P. Wang, J. Yu, J. Phys. Chem. C 120 (2016) 3722–3730.
[862] S.-Z. Wu, K. Li, W.-D. Zhang, Appl. Surf. Sci. 324 (2015) 324–331. [913] H. Yu, H. Irie, Y. Shimodaira, Y. Hosogi, Y. Kuroda, M. Miyauchi, K.
[863] W. Zhao, Z. Wei, H. He, J. Xu, J. Li, S. Yang, C. Sun, Appl. Catal. A: Gen. 501 Hashimoto, J. Phys. Chem. C 114 (2010) 16481–16487.
(2015) 74–82. [914] X. Wang, R. Yu, P. Wang, F. Chen, H. Yu, Appl. Surf. Sci. 351 (2015) 66–73.
[864] Z. Xiu, H. Bo, Y. Wu, X. Hao, Appl. Surf. Sci. 289 (2014) 394–399. [915] P. Wang, Y. Xia, P. Wu, X. Wang, H. Yu, J. Yu, J. Phys. Chem. C 118 (2014)
[865] Z. Zhu, Z. Lu, D. Wang, X. Tang, Y. Yan, W. Shi, Y. Wang, N. Gao, X. Yao, H. 8891–8898.
Dong, Appl. Catal. B: Environ. 182 (2016) 115–122. [916] Q. Liu, Y. Guo, Z. Chen, Z. Zhang, X. Fang, Appl. Catal. B: Environ. 183 (2016)
[866] Q. Fan, Y. Huang, C. Zhang, J. Liu, L. Piao, Y. Yu, S. Zuo, B. Li, Catal. Today 264 231–241.
(2016) 250–256. [917] C. Zhao, M. Pelaez, X. Duan, H. Deng, K. O’Shea, D. Fatta-Kassinos, D.D.
[867] N. Tian, H. Huang, Y. Zhang, Appl. Surf. Sci. 358 (2015) 343–349. Dionysiou, Appl. Catal. B: Environ. 134 (2013) 83–92.
[868] Z. Li, S. Yang, J. Zhou, D. Li, X. Zhou, C. Ge, Y. Fang, Chem. Eng. J. 241 (2014) [918] L. Rizzo, D. Sannino, V. Vaiano, O. Sacco, A. Scarpa, D. Pietrogiacomi, Appl.
344–351. Catal. B: Environ. 144 (2014) 369–378.
[869] X.J. Wang, Q. Wang, F.T. Li, W.Y. Yang, Y. Zhao, Y.J. Hao, S.J. Liu, Chem. Eng. J. [919] H. Wang, Z. Ye, C. Liu, J. Li, M. Zhou, Q. Guan, P. Lv, P. Huo, Y. Yan, Appl. Surf.
234 (2013) 361–371. Sci. 353 (2015) 391–399.
[870] F. Chang, C. Li, J. Chen, J. Wang, P. Luo, Y. Xie, B. Deng, X. Hu, Superlattice [920] T. Inoue, A. Fujishima, S. Konishi, K. Honda, Nature 277 (1979) 637–638.
Microstruct. 76 (2014) 90–104. [921] S.N. Habisreutinger, L. Schmidt- Mende, J.K. Stolarczyk, Angew. Chem. Int.
[871] S.-Y. Chou, C.-C. Chen, Y.-M. Dai, J.-H. Lin, W.W. Lee, RSC Adv. 6 (2016) Ed. 52 (2013) 7372–7408.
33478–33491. [922] Y. Izumi, Coord. Chem. Rev. 257 (2012) 171–186.
[872] N. Tian, H. Huang, Y. Guo, Y. He, Y. Zhang, Appl. Surf. Sci. 322 (2014) [923] S.C. Roy, O.K. Varghese, M. Paulose, C.A. Grimes, ACS Nano 4 (2010)
249–254. 1259–1278.
[873] H. Li, J. Liu, W. Hou, N. Du, R. Zhang, X. Tao, Appl. Catal. B: Environ. 160 [924] X. Chang, T. Wang, J. Gong, Energy Environ. Sci. 9 (2016) 2177–2196.
(2014) 89–97. [925] L. Yuan, Y.-J. Xu, Appl. Surf. Sci. 342 (2015) 154–167.
[874] Y. Tian, B. Chang, J. Lu, J. Fu, F. Xi, X. Dong, ACS Appl. Mater. Interfaces 5 [926] M. Li, L. Zhang, X. Fan, Y. Zhou, M. Wu, J. Shi, J. Mater. Chem. A 3 (2015)
(2013) 7079–7085. 5189–5196.
[875] Y. Guo, J. Li, Z. Gao, X. Zhu, Y. Liu, Z. Wei, W. Zhao, C. Sun, Appl. Catal. B: [927] M. Li, L. Zhang, M. Wu, Y. Du, X. Fan, M. Wang, L. Zhang, Q. Kong, J. Shi, Nano
Environ. 192 (2016) 57–71. Energy 19 (2016) 145–155.
[876] C. Wen, H. Zhang, Q. Bo, T. Huang, Z. Lu, J. Lv, Y. Wang, Chem. Eng. J. 270 [928] Y. He, L. Zhang, M. Fan, X. Wang, M.L. Walbridge, Q. Nong, Y. Wu, L. Zhao, Sol.
(2015) 405–410. Energy Mater. Sol. Cells 137 (2015) 175–184.
[877] D. Chen, K. Wang, W. Hong, R. Zong, W. Yao, Y. Zhu, Appl. Catal. B: Environ. [929] H. Shi, G. Chen, C. Zhang, Z. Zou, ACS Catal. 4 (2014) 3637–3643.
166 (2015) 366–373. [930] S. Zhou, Y. Liu, J. Li, Y. Wang, G. Jiang, Z. Zhao, D. Wang, A. Duan, J. Liu, Y. Wei,
[878] Y. Shi, Z. Yang, Y. Liu, J. Yu, F. Wang, J. Tong, B. Su, Q. Wang, RSC Adv. 6 Appl. Catal. B: Environ. 158–159 (2014) 20–29.
(2016) 39774–39783. [931] Y. Wang, Y. Xu, Y. Wang, H. Qin, X. Li, Y. Zuo, S. Kang, L. Cui, Catal. Commun.
[879] J. Ding, L. Wang, Q. Liu, Y. Chai, X. Liu, W.-L. Dai, Appl. Catal. B: Environ. 176 74 (2016) 75–79.
(2015) 91–98. [932] M. Ovcharov, N. Shcherban, S. Filonenko, A. Mishura, M. Skoryk, V.
[880] K. Li, L. Yan, Z. Zeng, S. Luo, X. Luo, X. Liu, H. Guo, Y. Guo, Appl. Catal. B: Shvalagin, V. Granchak, Mat. Sci. Eng. B: Adv. 202 (2015) 1–7.
Environ. 156 (2014) 141–152. [933] X. Zhang, L. Wang, Q. Du, Z. Wang, S. Ma, M. Yu, J. Colloid Interface Sci. 464
[881] L. Huang, H. Xu, R. Zhang, X. Cheng, J. Xia, Y. Xu, H. Li, Appl. Surf. Sci. 283 (2016) 89–95.
(2013) 25–32. [934] Z. Tong, D. Yang, J. Shi, Y. Nan, Y. Sun, Z. Jiang, ACS Appl. Mater. Interfaces 7
[882] B. Korean, Chem. Soc. 36 (2015) 17–23. (2015) 25693–25701.
[883] S. Hu, L. Ma, F. Li, Z. Fan, Q. Wang, J. Bai, X. Kang, G. Wu, RSC Adv. 5 (2015) [935] W.-J. Ong, L.K. Putri, L.-L. Tan, S.-P. Chai, S.-T. Yong, Appl. Catal. B: Environ.
90750–90756. 180 (2016) 530–543.
[884] Y. Sun, T. Xiong, Z. Ni, J. Liu, F. Dong, W. Zhang, W.-K. Ho, Appl. Surf. Sci. 358 [936] L.K. Putri, W.-J. Ong, W.S. Chang, S.-P. Chai, Catal. Sci. Technol. 6 (2016)
(2015) 356–362. 744–754.
[885] Z. Jin, N. Murakami, T. Tsubota, T. Ohno, Appl. Catal. B: Environ. 150 (2014) [937] Y. Huang, Y. Wang, Y. Bi, J. Jin, M.F. Ehsan, M. Fu, T. He, RSC Adv. 5 (2015)
479–485. 33254–33261.
[886] J. Ma, C. Wang, H. He, Appl. Catal. B: Environ. 184 (2016) 28–34. [938] J. Qin, S. Wang, H. Ren, Y. Hou, X. Wang, Appl. Catal. B: Environ. 179 (2015)
[887] F. Chang, Y. Xie, C. Li, J. Chen, J. Luo, X. Hu, J. Shen, Appl. Surf. Sci. 280 (2013) 1–8.
967–974. [939] X. Yang, W. Xin, X. Yin, X. Shao, Chem. Phys. Lett. 651 (2016) 127–132.
[888] W. Tian, N. Li, J. Zhou, Appl. Surf. Sci. 361 (2016) 251–258. [940] J. Fu, S. Cao, J. Yu, J. Low, Y. Lei, Dalton Trans. 43 (2014) 9158–9165.
[889] Q. Wang, L. Zheng, Y. Bai, J. Zhao, F. Wang, R. Zhang, H. Huang, B. Su, Appl. [941] J. Yu, J. Low, W. Xiao, P. Zhou, M. Jaroniec, J. Am. Chem. Soc. 136 (2014)
Surf. Sci. 347 (2015) 602–609. 8839–8842.
[890] G. Xin, Y. Meng, J. Chem. N. Y. 2013 (2013) 1–5. [942] Q. Xu, J. Yu, J. Zhang, J. Zhang, G. Liu, Chem. Commun. 51 (2015) 7950–7953.
[891] Y. Ke, H. Guo, D. Wang, J. Chen, W. Weng, J. Mater. Res. 29 (2014) 2473–2482. [943] J. Ge, K. Deng, W. Cai, J. Yu, X. Liu, J. Zhou, J. Colloid Interface Sci. 401 (2013)
[892] Y. Meng, G. Xin, D. Chen, Optoelectron. Adv. Mater. 5 (2011) 648–650. 34–39.
[893] Y. Meng, J. Shen, D. Chen, G. Xin, Rare Met. 30 (2011) 276–279. [944] W.Q. Cai, Y.Z. Hu, J.G. Yu, W.G. Wang, J.B. Zhou, M. Jaroniec, RSC Adv. 5
[894] Y. Liu, X. Yuan, H. Wang, X. Chen, S. Gu, Q. Jiang, Z. Wu, L. Jiang, Y. Wu, G. (2015) 7066–7073.
Zeng, Catal. Commun. 70 (2015) 17–20. [945] J. Yu, Y. Le, B. Cheng, RSC Adv. 2 (2012) 6784–6791.
[895] Q. Wang, Y. Shi, Z. Du, J. He, J. Zhong, L. Zhao, H. She, G. Liu, B. Su, Eur. J. [946] F. Su, S.C. Mathew, L. Moehlmann, M. Antonietti, X. Wang, S. Blechert,
Inorg. Chem. (2015) 4108–4115. Angew. Chem. Int. Ed. 50 (2011) 657–660.
[896] T. Xian, H. Yang, L.J. Di, J.F. Dai, J. Alloy Compd. 622 (2015) 1098–1104. [947] Z.J. Wang, K. Garth, S. Ghasimi, K. Landfester, K.A.I. Zhang, ChemSusChem 8
[897] X. Gao, X. Jiao, L. Zhang, W. Zhu, X. Xu, H. Ma, T. Chen, RSC Adv. 5 (2015) (2015) 3459–3464.
76963–76972. [948] L. Song, S. Zhang, X. Wu, H. Tian, Q. Wei, Ind. Eng. Chem. Res. 51 (2012)
[898] Z. Li, B. Li, S. Peng, D. Li, S. Yang, Y. Fang, RSC Adv. 4 (2014) 35144–35148. 9510–9514.
[899] S. Fang, K. Lv, Q. Li, H. Ye, D. Du, M. Li, Appl. Surf. Sci. 358 (2015) 336–342. [949] X. Xiao, J. Jiang, L. Zhang, Appl. Catal. B: Environ. 142 (2013) 487–493.
[900] H. Pan, X. Li, Z. Zhuang, C. Zhang, J. Mol. Catal. A: Chem. 345 (2011) 90–95. [950] X. Chen, J. Zhang, X. Fu, M. Antonietti, X. Wang, J. Am. Chem. Soc. 131 (2009)
[901] W. Chen, G.-R. Duan, T.-Y. Liu, S.-M. Chen, X.-H. Liu, Mater. Sci. Semicond. 11658–11659.
Process. 35 (2015) 45–54.
 J. Wen et al. / Applied Surface Science 391 (2017) 72–123 123

[951] G.D. Ding, W.T. Wang, T. Jiang, B.X. Han, H.L. Fan, G.Y. Yang, ChemCatChem 5 [965] R.S. Sprick, B. Bonillo, R. Clowes, P. Guiglion, N.J. Brownbill, B.J. Slater, F.
(2013) 192–200. Blanc, M.A. Zwijnenburg, D.J. Adams, A.I. Cooper, Angew. Chem. Int. Ed. 55
[952] T. Fu, P. Hu, T. Wang, Z. Dong, N. Xue, L. Peng, X. Guo, W. Ding, Chin. J. Catal. (2016) 1824–1828.
36 (2015) 2030–2035. [966] Z.J. Wang, S. Ghasimi, K. Landfester, K.A.I. Zhang, Chem. Commun. 50 (2014)
[953] G. Shiravand, A. Badiei, G.M. Ziarani, M. Jafarabadi, M. Hamzehloo, Chin. J. 8177–8180.
Catal. 33 (2012) 1347–1353. [967] B.C. Ma, S. Ghasimi, K. Landfester, F. Vilela, K.A.I. Zhang, J. Mater. Chem. A 3
[954] X. Ye, Y. Cui, X. Qiu, X. Wang, Appl. Catal. B: Environ. 152 (2014) 383–389. (2015) 16064–16071.
[955] X. Ye, Y. Cui, X. Wang, ChemSusChem 7 (2014) 738–742. [968] P. Bornoz, M.S. Prevot, X. Yu, N. Guijarro, K. Sivula, J. Am. Chem. Soc. 137
[956] P. Zhang, Y. Gong, H. Li, Z. Chen, Y. Wang, RSC Adv. 3 (2013) 5121–5126. (2015) 15338–15341.
[957] M. Potowski, J.O. Bauer, C. Strohmann, A.P. Antonchick, H. Waldmann,
Angew. Chem. Int. Ed. 51 (2012) 9512–9516.
[958] H. Zhan, W. Liu, M. Fu, J. Cen, J. Lin, H. Cao, Appl. Catal. A: Gen. 468 (2013)
184–189.
[959] P. Zhang, Y. Wang, J. Yao, C. Wang, C. Yan, M. Antonietti, H. Li, Adv. Synth.
Catal. 353 (2011) 1447–1451.
[960] X.-H. Li, M. Baar, S. Blechert, M. Antonietti, Sci. Rep. U. K. 3 (2013).
[961] J. Huang, W. Ho, X. Wang, Chem. Commun. 50 (2014) 4338–4340.
[962] C. Su, R. Tandiana, B. Tian, A. Sengupta, W. Tang, J. Su, K.P. Loh, ACS Catal. 6
(2016) 3594–3599.
[963] Q. Zhou, G. Shi, J. Am. Chem. Soc. 138 (2016) 2868–2876.
[964] S. Ghosh, N.A. Kouame, L. Ramos, S. Remita, A. Dazzi, A. Deniset- Besseau, P.
Beaunier, F. Goubard, P.-H. Aubert, H. Remita, Nat. Mater. 14 (2015)
505–511.