Microporous and Mesoporous Materials 220 (2016) 247e252

Contents lists available at ScienceDirect

Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Enhancement in CO2 adsorption capacity and selectivity in the

chalcogenide aerogel CuSb2S4 by post-synthetic modification with LiCl
Ejaz Ahmed, Alexander Rothenberger*
Physical Sciences and Engineering Division, King Abdullah University of Science and Technology Thuwal, Kingdom of Saudi Arabia

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

Article history: The new chalcogel CuSb2S4 was obtained by reacting Cu(OAc)2$H2O with KSbS2 in a water/formamide
Received 22 June 2015 mixture at room temperature. In order to modify the gas adsorption capacity the synthesized CuSb2S4
Received in revised form aerogel was loaded with different amounts of LiCl. CO2 adsorption measurements on the CuSb2S4 aerogel
2 September 2015
before and after treatment with LiCl showed more than three times increased uptake of the LiCl-
Accepted 5 September 2015
modified chalcogel. The selectivities of the gas pairs CO2/H2 and CO2/CH4 in the LiCl-treated chalcogel
Available online 11 September 2015
are 235 and 105 respectively and amongst the highest reported for chalcogenide-based aerogels. In
comparison with other porous materials like zeolites, activated carbon and most of the Metal Organic
Keywords:
Adsorption
Frameworks (MOFs) or Porous Organic Frameworks (POFs), our synthesized aerogels show good air and
Carbon dioxide moisture stability. Although, the CO2 storage capacity of our aerogels is relatively low, however the
Chalcogel selectivity of CO2 over H2 or CH4 in LiCl-loaded aerogels are higher than in zeolites, activated carbon as
Mesoporous materials well as some MOFs like Cu-BTC and MOF-5 etc.
© 2015 Elsevier Inc. All rights reserved.

1. Introduction show high adsorption capacity and selectivity for CO2

[18,19,22,27,28].
The CO2 capture and sequestration (CCS) has recently received For high CO2/H2 or CO2/CH4 adsorption selectivity, bonding
significant attention [1,2]. In addition to the negative effects on interactions between porous material and CO2 are crucial.
climate, CO2 is a major contaminant of methane-rich gases and Numerous post-synthetic modifications (PSM) on porous mate-
hydrogen fuels [2,3]. Porous CO2 capture materials usually exhibit a rials have been performed to enhance the interactions between
high surface area and pore volume together with adsorptive-CO2 adsorbent and gas molecules [5,12,13,29e31]. For instance, CO2
bonding interactions that result in high CO2 adsorption capacity adsorption capacity has been improved in amine-functionalized
disadv. [4,5]. The traditional CO2 capture is based on the chemical ab- zeolites and ion-exchanged zeolites while nitrogen-doped
of amine sorption of CO2 using aqueous solutions of amines [4,6]. However, a porous carbons have also shown an excellent CO2 uptake
large amount of energy is prerequisite for amine regeneration [4,6]. [29,30]. Similarly, some MOFs have demonstrated a notable
absorption
Several porous materials have been studied for CO2 uptake capacity, improvement in CO2 adsorption capacity and selectivity via the
such as zeolites [7,8], activated carbon [9e11], MOFs [12] and POFs introduction of flexible pendants bearing hydroxyl, amine, or
Advan or porous aromatic frameworks (PAFs) [4,13]. Due to their high ether functional groups [31]. Moreover, impregnation of certain
of specific surface areas and less energy consumption for regenera- metal ions onto the surface of the porous networks has improved
tion, they are considered for CO2 capture [7e13]. The adsorption
conventional the gas adsorption efficiency [4,5,12,13]. Incorporating metal ions
material behaviour of porous metal chalcogenides (chalcogels) with high has attracted considerable attention because they can increase the
surface area, large pore size distribution, surface polarizability, and heat of adsorption for CO2. The uniform dispersion of metal ions
chemical selectivity has also been studied in this context [14e26]. over the substrate/adsorptive surface is achieved by treatment
Current investigations have demonstrated that metal chalcogels with a metal salt solution, followed by drying under vacuum
[3e5,13,31a]. Recently, De Lange and Lane have demonstrated that
LiCl shows one of the strongest interactions with the quadrupole
moment of CO2 (DHads ~ 38 kJ/mol) [32]. Taking into account that
LiCl has a relatively low melting point in accordance with the
* Corresponding author. Tel.: þ966 128080745; fax: þ966 128021258.
definition of the Tammann temperature (the point at which the
E-mail address: [email protected] (A. Rothenberger).

http://dx.doi.org/10.1016/j.micromeso.2015.09.010
1387-1811/© 2015 Elsevier Inc. All rights reserved.
248 E. Ahmed, A. Rothenberger / Microporous and Mesoporous Materials 220 (2016) 247e252

metal salt starts to diffuse in a solid matrix), this alkali metal salt 2.3. Transmission electron microscopy (TEM)
was considered a suitable candidate for dispersion [33]. For
instance, introducing dispersed alkali metal cations, especially Liþ The chalcogels samples for TEM were prepared by suspending
ions, into MOFs, POFs or PAFs improved CO2 and H2 storage ca- the powder aerogel samples in ether and casting on a carbon-
pacities [2,4,5,12,13,31,33]. Recent investigations have shown that coated Cu grid. Finally, high-resolution TEM images were ob-
the incorporation of light-harvesting dyes in chalcogels can tained using a FEI Titan 80e300 Super Twin operated at 300 kV.
enhance the photochemical production of H2 [24e26]. Until now,
however, there appear to be no studies about the post-synthetic 2.4. Scanning electron microscopy/energy dispersive X-ray
modifications of metal chalcogels to improve their CO2 adsorp- spectroscopy (SEM/EDS)
tion capacity and selectivity.
Motivated by the above-mentioned experimental and theoret- Quanta 3D FEG was used for SEM images and EDS of the aerogel
ical studies, the new chalcogenide aerogel CuSb2S4 was synthesized samples.
and treated with LiCl. The synthesis of CuSb2S4 and effects of the
LiCl treatment on the gas adsorption properties are reported in the 2.5. Inductively Coupled Plasma-Optical Emission spectroscopy
following. (ICP-OES) analysis

To determine the elemental compositions of chalcogel samples,

2. Experimental powder aerogels were first suspended in water, and then the
samples were digested in 6.0 mL of 69% nitric acid in closed volu-
2.1. Synthesis metric flasks using an Ethos1 microwave digestion system at 493 K
until the whole solid was completely dissolved. Accurate de-
Starting materials were commercial sulfur (Alfa Aesar, terminations of Cu, Sb, S, and Li concentrations were performed on
99.9995%), antimony (Strem Chemicals, 99.998%), potassium a Varian 720-ES ICP-OES instrument.
(Strem Chemicals, 99%), copper (II) acetate monohydrate (Strem
Chemicals, 99% anhydrous), formamide (Sigma, 99.5%), ethanol 2.6. UV/VIS spectroscopy
(Aldrich, 99.8%). High purity gases (N2, CO2, CH4 and H2) were ob-
tained from Abdullah Hashim Industrial Gases & Equipment Co. The UV/Vis diffuse reflectance spectrum was recorded with an
Ltd. The ternary phase KSbS2 was prepared by reacting K2S and Agilent Cary 5000 spectrometer in the wavelength range of
Sb2S3 in stoichiometric ratio at 850 K (100/K/h heating rate, 96 h 200e3000 nm. BaSO4 powder was used as a reference (100%
soaking at 850 K, cooling to RT in 3d) (supporting information, reflectance) material and for dilution.
Fig. S1a) [34a]. The solvents (formamide and water) were deoxy-
genated with N2 gas for about 2 h. Synthesis and solvent exchange 2.7. Thermogravimetric analysis (TGA)
were carried out in a N2-glovebox.
The TGA measurements were performed on a Netzsch STA 449
F3 thermogravimetric analyzer using a heating rate of 20 K/min
2.1.1. Synthesis of the CuSb2S4 chalcogel
under N2 flow (20 mL/min).
100 mg (0.50 mmol) of Cu(CH3CO2)2$H2O was dissolved in
8.0 mL of deionized H2O. The aqueous solution of copper acetate
2.8. Density measurements
was slowly added with stirring to a dark red solution of 225 mg
(1.0 mmol) of KSbS2 in 8.0 mL of formamide. The reaction mixture
The skeletal densities of the aerogel materials were determined
was left at room temperature undisturbed for one week in order to
by a Micromeritics AccuPyc 1340 gas pycnometer using ultra high
allow gel formation. After one week, a black CuSb2S4 rigid chalcogel
purity helium gas.
was obtained and solvent exchange was carried out with a 50:50
mixture of ethanol/water 7 times. Treatment of the gel then
2.9. Powder diffraction measurements
involved washings with absolute ethanol over a week followed by
supercritical CO2 drying. After critical point drying, the obtained
The powder diffraction patterns were measured with a Stoe
aerogel consists of very fluffy black particles.
STADI MP Powder diffractometer, equipped with a Mythen 1K sil-
icon strip detector covering 80 in 2q and using Cu-Ka1 radiation.
2.1.2. Synthesis of LiCl-loaded chalcogels The calibration was done with a silicon standard and the samples
For the synthesis of 4wt % LiCl@CuSb2S4 chalcogel, 200 mg of the were analyzed at 293(2) K. The diffraction patterns (raw data) were
CuSb2S4 aerogel was immersed in a 25 mL of a 0.2 M LiCl/ethanol compared to the simulated phases deposited in the Fachinforma-
solution with stirring at room temperature for 24 h. After filtration, tionszentrum Karlsruhe, Germany (Findit, release 2014).
the LiCl-loaded gel undergoes supercritical CO2 drying. For the
synthesis of 7.5wt % LiCl@CuSb2S4 chalcogel, a similar procedure 2.10. Adsorption measurements
was used (0.4 M LiCl ethanol solution).
All physisorption measurements were performed on a Micro-
meritics ASAP 2020 HD instrument with Kalrez modification.
2.2. Supercritical drying Nitrogen. Nitrogen adsorption and desorption isotherms were
performed at 77 K. About 100e200 mg of sample was used for each
Critical point drying of the unmodified and LiCl-loaded chalco- analysis. The samples were degassed at 348 K under vacuum
gels was carried out with a Tousimis Autosamdrie815B instrument. (<104 mbar) for 10 h before the analysis. Low pressure incre-
The sample was soaked with liquid carbon dioxide and depending mental dosing of 0.1338 mmol/g (STP) and 30s equilibration were
on the amount of the gel, the soaking time and exchange time applied as analysis conditions. BET transform plot were obtained in
varies. Finally, aerogels were obtained after supercritical drying at the 0.05 to 0.35 [34b] relative pressure (P/Po) regions and corre-
35  C. lation coefficient of 0.99999 was obtained in all of the cases while
 E. Ahmed, A. Rothenberger / Microporous and Mesoporous Materials 220 (2016) 247e252 249

the distribution of pore sizes was calculated using the Bar- supporting information, Fig. S7). The similarity in appearance of
retteJoynereHalenda (BJH) model. CuSb2S4 and LiCl-loaded aerogels indicates that the structure of the
Hydrogen, Methane, and Carbon Dioxide. A Julabo HE digital parent system is preserved after loading. The porosity of the
chiller system was used for each measurement at 273 K and 263 K CuSb2S4 and LiCl-loaded aerogels was studied by physical nitrogen
equipped with a cryogenic water bath (50:50 vol % water-ethylene adsorption at 77 K. The nitrogen adsorption and desorption iso-
glycol mixture). Low-pressure incremental dosing of 0.022 mmol/g therms of the prepared aerogels exhibit the type IV adsorption
(STP) and 60 s of equilibration were used for each analysis. branch with a combination of H1 and H3 hysteresis loops typical of
a primarily mesoporous system (Fig. 1a and supporting information
3. Results and discussion Fig. S8a) [34c].
The BJH plots of pore size distribution show broad ranges of
The chalcogenide aerogel (chalcogel) CuSb2S4 was synthesized pores (Fig. 1b and supporting information Fig. S8b) with ~80% of the
by a metathesis reaction containing the 1:2 ratios of copper linker pores in the mesoporous range; therefore the synthesized aerogels
and thioantimonate building block (Scheme 1). After gel formation, are predominantly mesoporous materials. The Bru-
solvent exchange removed formamide and by-products from the nauereEmmetteTeller (BET) surface area of the aerogel CuSb2S4 is
inorganic framework. Supercritical CO2 drying of the solvent- 412 m2/g. Incorporation of LiCl caused a small reduction in the BET
exchanged CuSb2S4 is essential to extract liquid components surface area (Table 1). The BET surface areas of the aerogels are
whilst retaining the porosity of the chalcogels [20e22,27,28]. decreasing with increasing LiCl contents. For 1LiCl@CuSb2S4 (LiCl
content is 4 wt%), the BET has been reduced from 412 m2/g to
3.1. Characterization 371 m2/g while a further reduction to 303 m2/g has been observed
in higher LiCl content aerogel 2LiCl@CuSb2S4 (LiCl content is 7.5 wt
Multiple EDS analyses showed the elemental compositions close
to the stoichiometric ratios i.e., Cu1.0Sb1.95S3.99 (supporting in-
formation, Fig. S2). This confirms that Cu2þ cations and [SbS2]e
anions form a charge-balanced gel network. The CuSb2S4 aerogel is
further characterized by PXRD which shows that the product is
amorphous (supporting information, Fig. S1b). The presence of
Cu(II) in the aerogel was confirmed by XPS (supplementary mate-
rial, Fig. S15). The TGA shows that decomposition of CuSb2S4 starts
at a temperature of 217  C under nitrogen atmosphere (supporting
information, Fig. S5a), suggesting that the material possesses good
thermal stability. After LiCl loading, a slight improvement in ther-
mal stability has been observed (supporting information, Fig. S5b).
The optical energy band gap of the aerogel was determined by the
diffuse reflectance solid-state spectroscopy. The band gap shows a
value of 1.75 eV (supporting information, Fig. S6). It has been
observed that the aerogel CuSb2S4 is insoluble in common organic
solvents, such as THF, acetone, ethanol, and DMF, indicating high
chemical stability. After suspending the aerogel in LiCl-ethanol
solution, two different lithium derivatives were obtained, i.e.,
1LiCl@CuSb2S4 and 2LiCl@CuSb2S4 containing LiCl contents of 4 wt
% and 7.5 wt% respectively. The incorporation of LiCl has been
confirmed by ICP-OES and EDS (supporting information Fig. S3-4,
Table S1-2). The PXRD patterns of the LiCl-loaded aerogels also
show the presence of LiCl along with a dominant amorphous phase
(supporting information, Fig. S1b-c). The morphologies of the
CuSb2S4 aerogel and LiCl-loaded aerogels 1LiCl@CuSb2S4 and
2LiCl@CuSb2S4 were investigated by electron microscopy. The TEM
images show that the unmodified aerogel and LiCl-modified aero-
gels show the interlinked porous particle nature (Fig. 1aeb and

Fig. 1. Characterization and properties of the CuSb2S4 gel: a) Low magnification TEM
image showing porosity (inset) with N2 adsorption-desorption isotherm, b) Pore-size
Scheme 1. Photographic illustration of the synthesis of CuSb2S4 aerogel; (a) aqueous (VeD) distribution plot calculated from the adsorption isotherm by the BJH method
solution of copper(II) acetate, (b) KSbS2 (inorganic building block) solution in form- along with a high magnification TEM image showing amorphous nature by electron
amide (FM), (c) completed metathesis reaction yielding a black chalcogel CuSb2S4. diffraction (inset).
250 E. Ahmed, A. Rothenberger / Microporous and Mesoporous Materials 220 (2016) 247e252

Table 1
Properties of the aerogels with respect to their surface area, porosity and skeletal density.

Adsorbent BET (m2/g) Average pore size (nm) Pore volume (cm3/g) Density (g/cm3)

CuSb2S4 412 16.07 1.655 1.34

1LiCl@CuSb2S4 371 13.48 1.252 1.89
2LiCl@CuSb2S4 303 9.74 0.737 2.26

%) (Table 1). A slight decrease in the pore volume and pore width is supporting information Fig. S9). The metal chalcogenide aerogel
also attributed to the incorporation of the lithium chloride species. surface can interact strongly with CO2 due to its polarizable nature
A considerable increase of the density after lithiation causes a [18,19,22,27,28]. In comparison with CH4 and H2, CO2 is more
noticeable decrease in the pore volume (Table 1). It is assumed that polarizable (polarizability a in units of 1024 cm3: a (CO2) ¼ 2.9 >a
the impregnation of LiCl on the surface of the aerogel at room (CH4) ¼ 2.6 >a (H2) ¼ 0.8) and their adsorption can be explained by
temperature have some physical interaction rather than any the interaction of CO2 with the sulfidic surface through dispersion
chemical bonding because after multiple washings with water and forces. Fig. 2a shows that the CO2 uptake of CuSb2S4 is about
ethanol, LiCl can be easily removed. 0.63 mmol/g at 273 K, while 2LiCl@CuSb2S4 shows a maximum CO2
uptake of 2.31 mmol/g at 273 K, which is remarkably increased by
~360%, compared with the unmodified chalcogel. It indicates that
3.2. Adsorption studies
the CO2 uptake is increasing with more LiCl content introduced into
the aerogel structure. On the other hand, when the LiCl content is
The gas uptake capacities of CuSb2S4 and LiCl-loaded chalcogels
were investigated for CO2, CH4 and H2 at 273 K and 263 K (Figs. 2e3,

Fig. 3. a) CH4 adsorption isotherm at 273 K in the unmodified and Li-modified aero-
Fig. 2. CO2 and H2 adsorption isotherms at 273 K in the unmodified and LiCl-modified gels, b) a comparison of CO2, CH4 and H2 adsorption capacities in 2LiCl@CuSb2S4 at
aerogels. 273 K.
 E. Ahmed, A. Rothenberger / Microporous and Mesoporous Materials 220 (2016) 247e252 251

larger than 7.5 wt%, the CO2 uptake decreases noticeably (sup- 0.023 mmol/g at 273K, while the H2 uptake was found to be
porting information Fig. S8c). This is due to lithium chloride ag- 0.031 mmol/g and 0.038 mmol/g in 1LiCl@CuSb2S4 and 2LiCl@-
gregation on the surface, which reduces the pore size and surface CuSb2S4 respectively. Similarly a slight increment in the adsorption
area for adsorption (supporting information Table S3). The inter- capacity of CH4 (from 0.05 to 0.18 mmol/g) was also observed in the
action of guest molecules with host materials is usually evaluated LiCl-loaded aerogels. Moreover, the DHads are calculated from the
by the isosteric heat of adsorption DHads [4,5,13,33]. Fig. 4b shows H2 and CH4 adsorption data (supporting information, Fig. S10). We
that LiCl-loaded gels 1LiCl@CuSb2S4 and 2LiCl@CuSb2S4 have larger observed that the DHads of LiCl-loaded aerogels are higher than that
DHads for CO2 than that of CuSb2S4. Since the LiCl-loading causes a of CuSb2S4. This suggests that the Li ions in the modified aerogel
reduction in the surface area and pore volume, the enhanced CO2 promote strong mutual interactions between gas molecules and the
uptake (Fig. 3b) could be assigned to the presence of the LiCl in the chalcogel framework.
chalcogel framework. It is proposed that the dispersion of the From the adsorption isotherms of CO2, CH4 and H2, the
lithium species can create a high electric field on the framework adsorption selectivity of an equimolar gas mixture in the chalcogel
surface, which leads to a high binding force with quadrupolar CO2 has been calculated according to the ideal adsorbed solution theory
molecules [5,33]. (IAST; Figs. 2e4, supporting Information, Fig. S11-14, Table S4e5)
As far as the H2 and CH4 adsorption capacities are concerned, the [19,22,27]. The calculations revealed that the selectivities of the gas
LiCl-loaded aerogels also show a slight enhancement in the H2 and pairs CO2/H2 and CO2/CH4 in 2LiCl@CuSb2S4 are 235 and 105
CH4 uptake (Fig. 2b and 3a). Fig. 2b shows hydrogen adsorption respectively. This represents a large difference in the adsorbed
isotherms for CuSb2S4 and LiCl-loaded aerogels at 273 K. Based on amount of CO2 in comparison to H2 or CH4. Consequently, the se-
the isotherms, the H2 uptake of CuSb2S4 is calculated to be lectivities of the gas pairs CO2/H2 and CO2/CH4 have been enhanced
more than three times, amongst the highest reported for the
chalcogenide-based aerogels and most of the porous materials
(supporting Information, Table S6). Moreover, the synthesized
chalcogel is stable with respect to air and moisture according to XPS
results (Supporting information, Fig. S15). We have also studied the
adsorption-desorption cycles of hydrogen which shows almost
100% removal of H2 without any decomposition to our chalcogel
material (Supporting information, Fig. S16).

4. Conclusion

The chalcogel CuSb2S4 was synthesized by the solegel metath-

esis route and treatment with LiCl gave the Li-derivatives;
1LiCl@CuSb2S4 and 2LiCl@CuSb2S4. The 2LiCl@CuSb2S4 aerogel ex-
hibits the highest CO2 adsorption capability and gas selectivity
(CO2/H2 ¼ 235 and CO2/CH4 ¼ 105). The observed selectivities of the
gas pairs in the modified aerogels are remarkable and higher than
corresponding values in other chalcogels. Additionally the selec-
tivities of the gas pairs in LiCl-loaded aerogels are higher than in
zeolites as well as some MOFs like Cu-BTC and MOF-5 etc [35e38]
(supporting Information, Table S6). The CO2 uptake capacity de-
pends on the LiCl contents of the materials, which can be
customized by changing the amounts of lithium salt.
The development of high-performance porous chalcogenide
frameworks with high CO2/H2 and CO2/CH4 selectivity and
increased adsorption capacity of CO2 shows that further enhanced
material properties can be expected by post-synthetic treatment of
metal chalcogenide aerogels.

Acknowledgements

Electron microscope imaging work (TEM, SEM) was performed

in the Advanced Nanofabrication, Imaging and Characterization
Core Lab at KAUST, while the ICP-OES analysis was carried out in the
Analytical Core Lab at KAUST. We are grateful to Mr. V. Q. Wang and
Ms. N. Wei for TEM images as well as Dr M. N. Hedhili for XPS
measurements. This research was supported by the King Abdullah
University of Science and Technology baseline funding.

Fig. 4. Selectivity of the gas pairs CO2 over H2 and CO2 over CH4 in CuSb2S4 and Appendix A. Supplementary data
2LiCl@CuSb2S4 as predicted by the ideal adsorbed solution theory (IAST) for equimolar
mixtures of CO2/H2 and CO2/CH4 at 273 K (Ptotal is the total pressure of the gas
mixture), b) A comparison of heat of adsorption for CO2 calculated in CuSb2S4, Supplementary data related to this article can be found at http://
1LiCl@CuSb2S4 and 2LiCl@CuSb2S4. dx.doi.org/10.1016/j.micromeso.2015.09.010.
252 E. Ahmed, A. Rothenberger / Microporous and Mesoporous Materials 220 (2016) 247e252

References [23] B.D. Yuhas, C. Prasittichai, J.T. Hupp, M.G. Kanatzidis, J. Am. Chem. Soc. 133
(2011) 15854e15857.
[24] Y. Shim, B.D. Yuhas, S.M. Dyar, A.L. Smeigh, A.P. Douvalis, M.R. Wasielewski,
[1] S. Chu, Science 325 (2009) 1599.
M.G. Kanatzidis, J. Am. Chem. Soc. 135 (2013) 2330e2337.
[2] D.M. D'Alessandro, B. Smit, J.R. Long, Angew. Chem. Int. Ed. 49 (2010)
[25] Y. Shim, R.M. Young, A.P. Douvalis, S.M. Dyar, B.D. Yuhas, T. Bakas,
6058e6082.
M.R. Wasielewski, M.G. Kanatzidis, J. Am. Chem. Soc. 136 (2014)
[3] Y.-S. Bae, B.G. Hauser, O.K. Farha, J.T. Hupp, R.Q. Snurr, Microporous Meso-
13371e13380.
porous Mater 141 (2011) 231e235.
[26] B.D. Yuhas, A.L. Smeigh, A.P.S. Samuel, Y. Shim, S. Bag, A.P. Douvalis,
[4] H.P. Ma, H. Ren, X.Q. Zou, F.X. Sun, Z.J. Yan, K. Cai, D.Y. Wang, G.S. Zhu, J. Mater.
M.R. Wasielewski, M.G. Kanatzidis, J. Am. Chem. Soc. 133 (2011) 7252e7255.
Chem. A 1 (2013) 752e758.
[27] E. Ahmed, J. Khanderi, D.H. Anjum, A. Rothenberger, Chem. Mater 26 (2014)
[5] H.J. Park, M.P. Suh, Chem. Sci. 4 (2013) 685e690.
6454e6460.
[6] A.L. Chaffee, G.P. Knowles, Z.J. Liang, J. Zhang, P. Xiao, P.A. Webley, Int. J. Green
[28] (a) E. Ahmed, A. Rothenberger, Microporous Mesoporous Mater 199 (2014)
house Gas. Cont. 1 (2007) 11e18.
74e82;
[7] M. Palomino, A. Corma, J.L. Jorda, F. Rey, S. Valencia, Chem. Commun. 48
(b) E. Ahmed, A. Rothenberger, J. Mater. Chem. A 3 (2015) 7786e7792.
(2012) 215e217.
[29] V. Valtchev, G. Majano, S. Mintova, J. Perez-Ramirez, Chem. Soc. Rev. 42 (2013)
[8] M. Palomino, A. Corma, F. Rey, S. Valencia, Langmuir 26 (2010) 1910e1917.
263e290.
[9] V. Goetz, O. Pupier, A. Guillot, Adsorption-J. Int. Ads. Soc. 12 (2006) 55e63.
[30] (a) M. Sevilla, P. Valle-Vigon, A.B. Fuertes, Adv. Funct. Mater 21 (2011)
[10] M.B. Kim, Y.S. Bae, D.K. Choi, C.H. Lee, Ind. Eng. Chem. Res. 45 (2006)
2781e2787;
5050e5058.
(b) B. Ashourirad, A.K. Sekizkardes, S. Altarawneh, H.M. El-Kaderi, Chem.
[11] X. Peng, W.C. Wang, R.S. Xue, Z.M. Shen, Aiche J. 52 (2006) 994e1003.
Mater 27 (2015), http://dx.doi.org/10.1021/cm504435m.
[12] J. Liu, P.K. Thallapally, B.P. McGrail, D.R. Brown, J. Liu, Chem. Soc. Rev. 41
[31] (a) Q.L. Zhu, Q. Xu, Chem. Soc. Rev. 43 (2014) 5468e5512;
(2012) 2308e2322.
(b) L.L. Keenan, Doctoral Thesis, University of Bath, UK, 2014;
[13] K. Konstas, J.W. Taylor, A.W. Thornton, C.M. Doherty, W.X. Lim, T.J. Bastow,
(c) D.H. Hong, M.P. Suh, Chem. Eur. J. 20 (2014) 426e434.
D.F. Kennedy, C.D. Wood, B.J. Cox, J.M. Hill, A.J. Hill, M.R. Hill, Angew. Chem.
[32] K.M. de Lange, J.R. Lane, J. Chem. Phys. 135 (2011) 064304e064308.
Int. Ed. 51 (2012) 6639e6642.
[33] A.J. Hernandez-Maldonado, J. Guerrero-Medina, V.C. Arce-Gonzalez, J. Mater.
[14] I.U. Arachchige, S.L. Brock, J. Am. Chem. Soc. 128 (2006) 7964e7971.
Chem. A 1 (2013) 2343e2350.
[15] K.K. Kalebaila, D.G. Georgiev, S.L. Brock, J. Non-Cryst. Solids 352 (2006)
[34] (a) P.J. Olivier-Fourcade, E. Philippot, M. Maurin, Z. Anorg, Allg. Chem. 446
232e240.
(1978) 159e168;
[16] I.U. Arachchige, S.L. Brock, Acc. Chem. Res. 40 (2007) 801e809.
(b) I.F. Rouquerol, J. Rouquerol, K. Sing, Adsorption by Powders and Porous
[17] S. Bag, P.N. Trikalitis, P.J. Chupas, G.S. Armatas, M.G. Kanatzidis, Science 317
Solids: Principles, Methodology, and Applications, Academic Press, San Diego,
(2007) 490e493.
CA, 1999;
[18] S. Bag, A.F. Gaudette, M.E. Bussell, M.G. Kanatzidis, Nat. Chem. 1 (2009)
(c) K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol,
217e224.
T. Siemieniewska, Pure Appl. Chem. 57 (1985) 603e619.
[19] S. Bag, M.G. Kanatzidis, J. Am. Chem. Soc. 132 (2010) 14951e14959.
[35] Y. Belmabkhout, A. Sayari, Chem. Eng. Sci. 64 (2009) 3729e3735.
[20] Y. Oh, S. Bag, C.D. Malliakas, M.G. Kanatzidis, Chem. Mater 23 (2011)
[36] C.D. Boisgontier, J. Parmentier, A. Faour, J. Patarin, G.D. Pringruber, Energy &
2447e2456.
Fuels 24 (2010) 3595e3602.
[21] M. Shafaei-Fallah, J.Q. He, A. Rothenberger, M.G. Kanatzidis, J. Am. Chem. Soc.
[37] Q. Yang, C. Zhong, J. Phys. Chem. B 110 (2006) 17776e17783.
133 (2011) 1200e1202.
[38] Z.X. Zhao, Z. Li, Y.S. Lin, Ind. Eng. Chem. Res. 48 (2009) 10015e10020.
[22] M. Shafaei-Fallah, A. Rothenberger, A.P. Katsoulidis, J.Q. He, C.D. Malliakas,
M.G. Kanatzidis, Adv. Mater 23 (2011) 4857e4860.