Journal of Environmental Chemical Engineering 9 (2021) 106869

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Journal of Environmental Chemical Engineering

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

Recent advances in developing engineered biochar for CO2 capture: An

insight into the biochar modification approaches
Anis Natasha Shafawi a, Abdul Rahman Mohamed a, Pooya Lahijani b, *, Maedeh Mohammadi c
a
Low Carbon Economy (LCE) Research Group, School of Chemical Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang, Malaysia
b
School of Aerospace Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang, Malaysia
c
Faculty of Chemical Engineering, Babol Noshirvani University of Technology, 47148 Babol, Iran

A R T I C L E I N F O A B S T R A C T

Editor: Dr. Z. Wen Carbon dioxide (CO2) is the primary anthropogenic greenhouse gas with a significant contribution to global
warming; this excessive emission needs to be controlled through an effective carbon capture and storage (CCS)
Keywords: approach. Biochar has been considered a cost-effective adsorbent for CO2 capture; however, pristine biochar
Engineered biochar suffe from poor textural properties and surface chemistry. Here, developing engineered biochar requires careful
CO2 adsorption mechanism
tuning of the physicochemical properties of the biochar to obtain a high CO2 capture capacity. This work presents
Physical modification
a review of recent studies on the synthesis of engineered biochar through various modifications for CO2
Chemical treatment
Physicochemical modification adsorption. In this context, the impact of different modification approaches, including physical, chemical, and
Adsorption capacity physicochemical treatments, on the CO2 uptake properties of the engineered biochar are reviewed. Emphasis is
given to the mechanisms through which the CO2 adsorption capacity of biochar is enhanced after each modi­
fication. This survey of literature stresses the importance of maintaining a balance between the textural (specific
surface area and micropore volume) and surface chemical attributes (basicity, mineral content, various func­
tional groups, non-polarity and hydrophobicity) to produce engineered biochar with high CO2 uptake capacity,
strong selectivity towards CO2 over other gases and stable performance upon multiple cycles of CO2 adsorption-
desorption.

1. Introduction less than 2 ℃ above pre-industrial levels [6]. To achieve this target, CO2
emission must be substantially reduced.
Carbon dioxide (CO2) is one of the greenhouse gases (GHGs) that has Among the viable solutions to reduce CO2 emission is the capture of
led to extreme climate change, namely global warming [1]. From the CO2 from the emission sources before entering the atmosphere. In this
beginning of industrialization until the year 2018, the CO2 concentra­ context, carbon capture and storage (CCS) technologies have been
tion in the atmosphere increased from 280 to 408 ppm [2]. Based on the widely used, which can be categorized into three groups: pre-
prediction of the International Panel on Climate Change (IPCC), there combustion, post-combustion and oxy-fuel combustion capture sys­
will be a tremendous increment in the mean temperature of about 1.9 ℃ tems, as shown in Fig. 1 [7]. In the pre-combustion process, conven­
with a CO2 concentration of 570 ppm in the year 2100 [3]. Here, the tional fossil fuels such as coal or natural gas undergo partial oxidation
main activity that has considerably contributed to the increased level of with air or oxygen (O2), with or without steam, under high temperature
CO2 is the utilization of fossil fuels, which has highly affected the carbon and pressure to produce synthesis gas (syngas) or fuel gas, which is
balance of our planet [4]. Due to the growing society’s demand for en­ mainly composed of carbon monoxide (CO) and hydrogen (H2) [8].
ergy generation, it is impossible to stop the CO2 emission from the Then, the syngas is converted to H2 and CO2 via water-gas shift reaction
emission sources immediately; however, we have to implement some (CO + H2O ↔ CO2 + H2), where CO2 is separated from the gas, and only
strategies to reduce the emission of CO2 into the atmosphere to alleviate H2 will be available as a fuel for direct consumption in electric cars or
the impacts of global warming [5]. To control the emission of GHGs, an complete combustion to produce electricity using gas turbines [9]. Here,
agreement was reached in Paris with the involvement of 195 countries in CO2 is considered a by-product where the high pressure of the product
December 2015 that target to limit the global average temperature to gas stream facilitates the removal of CO2. The separated CO2 is

* Corresponding author.
E-mail address: [email protected] (P. Lahijani).

https://doi.org/10.1016/j.jece.2021.106869
Received 3 August 2021; Received in revised form 9 October 2021; Accepted 22 November 2021
Available online 26 November 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 1. CO2 capture technologies, including pre-combustion, oxy-fuel combustion and post-combustion capture systems. Copyright 2021 Springer.
Adapted with permission from [7].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

compressed and dehydrated before being transported for storage. The storage” AND “pre-combustion” OR “post-combustion” OR “oxy-fuel
principles of the pre-combustion process for different types of feedstock combustion”. The results are depicted in Fig. 2(a). To show the contri­
are similar; however, partial oxidation is a term used to describe bution of each technology to the CO2 capture over the last 15 years
pre-combustion of gaseous and liquid fuels, while gasification is a term (2005–2020), a pie diagram has been presented in Fig. 2(b), which
used for pre-combustion of solid fuels [8]. Technically, the applicability shows the considerably higher share of post-combustion CO2 capture
of the pre-combustion capture of CO2 is only limited to new fossil fuel research interest in CCS studies.
power plants [9]. The second approach, post-combustion CO2 capture, The most commonly used methods for post-combustion CO2 capture
involves the capture of dilute CO2 from the exhaust flue gas after the and separation are solvent absorption primarily using amine solution,
complete combustion of carbon-based fuel is conducted. The flue gas also known as amine scrubbing [14,15], CO2 adsorption using solid
usually goes through the denitrification and desulphurization units sorbents [16–19], membrane separation [20–22], cryogenic separation
before being sent for CO2 capture and separation [7]. Both pre- and [23–25] and CO2 bio-fixation using microalgae [26–28]. Among these,
post-combustion processes may involve the same feedstocks such as coal amine scrubbing and adsorption using solid sorbents have been mainly
or natural gas, but with different principles. Most power plants favor researched in CCS studies.
post-combustion CO2 capture due to its “end-of-pipe” characteristics, Significant industrial CO2 emission sources are natural gas and coal-
where CO2 is captured after a complete reaction [10]. In the oxy-fuel fired power plants, oil refineries, cement plants, and iron and steel
CO2 capture process, pure oxygen is used as the primary oxidant plants, whose contribution to the overall CO2 emission is shown in
instead of air. Here, the flue gas is mainly composed of CO2 with some Fig. 3. The current state of the art technique for capturing CO2 from
impurities such as SOx. The advantage of using this method is that easier these emission sources is amine scrubbing. This technology is already
purification can be achieved due to an oxygen-rich environment that mature and widely applied in many plants for gas purification due to its
produces a higher concentration of CO2 in the final flue gas [11]. high efficiency for CO2 absorption and separation [14,15].
However, oxy-fuel combustion is only suitable for a system that does not In the post-combustion CO2 capture, which is conducted at ambient
require the separation of CO2 and nitrogen (N2) [9]. Also, the supply of pressure, solid sorbents decorated with basic amine groups could pro­
pure oxygen is a big challenge due to the costly and energy-intensive vide a high CO2 uptake capacity [29]. Here, surface modification with
separation of oxygen from the air [7]. amine reagents can attach certain functional groups such as
By theory, among the three CCS technologies, pre-combustion could alkyl-amines to the solid surface to enhance the CO2 capture capacity
offer a 21–24 and 38–45% cheaper cost than oxy-fuel combustion and [30]. Examples of this are amine-functionalized silica [31],
post-combustion, respectively [12]. However, retrofitting the existing aminosilane-functionalized graphite [32], amine-functionalized meso­
facilities and addressing the technological issues impose additional costs porous zeolite [33], amine-functionalized mesoporous carbon [34] and
and complicate the step to commercialization. In terms of energy effi­ amine-functionalized metal-organic framework (MOF) [35] used for
ciency, oxy-fuel combustion is the most energy-efficient one among the
others, with a low energy-efficiency penalty (4%) compared with the
post-combustion route (8–12%) [7]. Yet, the employment of oxy-fuel
combustion in coal-fired power plants is slowing down due to the high
energy requirement of cryogenic air separation units used to supply high
purity oxygen [12]. Among the CCS technologies, post-combustion CO2
capture is the most mature and widely used technique for the reduction
of GHGs emissions [9]. However, dilution of CO2 by N2 from the air
decreases the partial pressure of CO2 and increases the cost for elec­
tricity generation by about 60–70% for new constructions and
220–250% for retrofitting [7]. The post-combustion CO2 capture targets
to achieve 90% CO2 removal with less than a 20% increase in the cost of
electricity; this corresponds to a CO2 separation and compression cost of
$ 30–50 per ton of CO2 [13].
To reflect the research and practical interests in CCS studies, the
Scopus database was used to retrieve the number of articles per year for
a period from 2005 to 2020 with the keywords “carbon capture and Fig. 3. Contribution of each CO2 emission source.

Fig. 2. (a) Number of articles per year for a period from 2005 to 2020 with the keywords “carbon capture and storage” AND “pre-combustion” OR “post-com­
bustion” OR “oxy-fuel combustion” and (b) contribution of each technology to the CO2 capture over the last 15 years (2005–2020).

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CO2 capture. Solid sorbents with basic amines were identified to have Table 1
high adsorption capacities due to the chemical interaction (such as the Various physical solid adsorbents for CO2 capture.
formation of carbamate) with CO2 and desirable desorption properties Solid adsorbent Activated carbons Zeolites MOFs
due to the easy regeneration [36,37]. In addition, amine-grafting pro­
Optimal operating 25–75 < 100 -78 to + 80
vides a larger surface area, thus eventually provides more active sites for temperature
higher CO2 adsorption capacity. Besides that, solid sorbents with basic (oC)
amine are tolerant to moisture, which means they are very selective for Optimal operating 1.45–145 1.45–145 1.4–440
CO2 capture even in the presence of water, and this is important for pressure (psi)
Primary CO2/CH4 CO2/N2 CO2/CH4
humid conditions [38]. Hence, it is difficult for other CO2 capture application in CO2/H2
technologies to compete economically with this process of reference. gas separation
However, amine solution is highly energy-consuming and expensive; it CO2 selectivity Medium Low High
chemically interacts with CO2 thus, makes the regeneration process CO2 adsorption Higher than zeolite at Medium High
capacity high pressures, which
difficult and inefficient, besides being corrosive to the equipment
decreases at low
[39–41]. Other than amine scrubbing, solid sorbents, which apply the pressure
concept of adsorption-driven separation technique, have attracted much Stability under Stable Unstable Unstable
interest due to the lower operating cost and ease of regeneration since humid
CO2 is only weakly adsorbed on the adsorbents through physical conditions
Synthesis cost $ 2.15/kg[51] $ 40–96/ ~$ 200/kg (MOF-
adsorption, predominantly van der Waals interaction [42,43]. It has kg[52] 5) and $130/kg
been estimated that the regeneration energy of monoethanolamine (MOF-177)[53]
(MEA), the most common solvent for CO2 capture, is 3.5 GJ per ton of
CO2 [44]. In a coal-fired power plant, the thermal efficiency reduced
from 35% (HHV basis) to 24.4% for 90% CO2 capture at the cost of $80 over other gas components at ambient conditions. In addition, the pro­
per ton CO2 removed. Although MEA chemisorption is the only duction of activated carbon involves some physical and/or chemical
commercialized method for CO2 capture, the expensive capital and activation of the parent char for the removal of some carbon atoms to
operation cost has even concluded the shutdown of some projects [7]. In create pores and some nooks and crannies in the structure of the
contrast to the chemical absorption of CO2, the regeneration energy for carbonaceous material [56]. These activations will impose additional
carbonaceous and non-carbonaceous physical adsorbents is lower, as no costs and complicate the management of chemical waste [57]. Although
new bonds are formed between CO2 and the adsorbent surface during activation of the char to obtain activated carbon increases its adsorption
the capture process resulting in less energy penalty for CO2 regeneration capacity, yet the product yield decreases with the degree of activation
[45]. Hence, the regeneration of solid sorbents demands less energy [58]. Therefore, research for the synthesis of solid sorbents with high
compared to the highly energy-intensive solvent recovery in the amine adsorption capacity and selectivity towards target gas, facile and
scrubbing method; besides, the solid sorbents do not cause any corrosion cost-effective preparation method, sustainable adsorption performance,
to the equipment [46]. and environmentally friendly nature is ongoing.
In general, an effective adsorbent must have high CO2 adsorption Thanks to the high availability and abundance of lignocellulosic
capacity and selectivity, fast adsorption-desorption kinetics, high sta­ residues and organic wastes, porous carbon adsorbents could be syn­
bility, and low production cost for large-scale applications. The most thesized from lignocellulosic biomass at a large scale and at a reasonable
typical solid adsorbents are zeolites, mesoporous oxides, MOFs and cost. Biochar, the immediate carbon-based solid product obtained
activated carbons and each of them has its own strengths and weak­ through thermochemical conversions of biomass, has potential appli­
nesses. Activated carbons are among the well-known carbonaceous cations in the fields of agriculture (for improvement of soil fertility),
physical adsorbents. The unique property of activated carbons is their climate change (adsorption of pollutant gases), environmental remedi­
slightly polar surface due to the presence of surface oxide groups, which ation (for adsorption of different contaminants from wastewater) and
enable them to adsorb more non-polar molecules such as CO2 [47]; material science (development of new materials to suit unique appli­
however, they have low CO2/N2 selectivity [45]. Zeolites have good cations) as shown in Fig. 4 [59–63]. From the economic point of view,
selectivity for CO2, yet they show poor adsorption performance in humid the break-even price of activated carbon is almost six times that of
environments [45]. MOFs, which are highly microcrystalline adsor­ biochar [61]. Furthermore, the energy demand for the production of
bents, possess high CO2 adsorption capacity at high pressures; never­ activated carbon is averagely 97 MJ/kg, which is almost 16 times higher
theless, their CO2 uptake is lower than other physical adsorbents at than the 6.1 MJ/kg required for biochar production [64]. It is also worth
atmospheric pressure [45]. Despite their high CO2 capture capacity and knowing that biochar production causes net negative GHGs emissions
selectivity, their large-scale manufacturing is costly; they are also un­ (− 0.9 kg CO2 equivalent per kg), whereas activated carbon production
stable under humid conditions [45,48]. Metal oxides such as calcium generates 6.6 kg CO2 equivalent per kg) [65]. With recent advancements
oxide (CaO) are widely used at an industrial scale due to their high in biochar production techniques, the biochar production cost is esti­
adsorption capacity. Yet, most of them drastically lose their adsorption mated in the range of $ 10–30/ton [66]. These estimates support the
capacity upon several cycles of CO2 capture [49,50]. Table 1 compares economic potential of biochar as a cost-effective adsorbent for various
various physical solid adsorbents for CO2 capture. The CO2 uptake ca­ applications.
pacity of these adsorbents, synthesized at different conditions and under The idea of using biochar for CO2 capture started after 2006 when
various operating conditions, have been reported in some comprehen­ charcoal was first identified as a suitable material to sequester carbon in
sive review papers [7,13,45]. the soil with a duration of up to thousands of years [67,68]. With this
In striving for new adsorbents to address the deficiencies of the ability, charcoal and biochar (char synthesized from biomass) have an
available ones, lots of hope has been pinned on porous carbon materials immense potential to reduce CO2 emissions into the atmosphere. So far,
with large surface area and tunable pore size, which are also highly biochar has been extensively used to raise soil fertility and agricultural
resistant to acidic, basic and humid environments [28,30]. Activated productivity [69]; however, studies have reported on the ability of
carbons present high CO2 adsorption capacity but relatively low selec­ biochar to reduce CO2 in the atmosphere even when presents in the soil
tivity towards CO2 compared to the other gases of the mixture (for [70].
example, H2O and N2) [55]. While the low pressure of flue gas (around Basically, biochar which is a carbon-rich product, can be obtained by
1 atm) and its low CO2 concentration (about 15 vol%) emphasize the heating the biomass in an inert atmosphere. The biomass can be con­
need for sorbents with high separation efficiency and selectivity for CO2 verted into biochar through various thermal processes such as pyrolysis,

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 4. Various applications of biochar in different areas.

gasification, torrefaction and hydrothermal carbonization [57,71–73]. A modifications involving physical, chemical, and physicochemical treat­
general assumption could be with the increase of the applied tempera­ ments have been implemented on the pristine biochar. Here, physical
ture, the energy consumption increases, yet biochar with better physi­ modification mainly focuses on improving the surface area and porosity
cochemical properties could be attained. In pyrolysis, no sophisticated properties of the biochar and tuning its pore size, which play a signifi­
equipment is needed for the synthesis of biochar. In a single-step cant role in physisorption. Many studies agree that physical interaction
carbonization process, the biomass is converted to biochar through is the major contributor to the CO2 capture capacity of the biochar [4,48,
heating in an inert atmosphere at the temperature range of 400–900 oC 78,79]. Hence, it is highly desired to produce biochar with a large
[57,74]. In the gasification process, the biomass is converted to biochar surface area and high microporosity, as these physical properties have
and other products (gaseous fuel and tar) in a controlled atmosphere been shown to play crucial roles in governing the adsorption [79,80]. A
involving a gasifying agent such as air, oxygen, steam, or any mixture of large surface area would increase the adsorption of CO2, and micropo­
them. This process is usually carried out at a high temperature of about rosity would be very beneficial for the adsorption of gas molecules [81].
750–1000 oC [75]. In torrefaction, which is a mild form of pyrolysis, the Yet, some studies concluded that chemical treatment could also enhance
conversion of biomass into biochar takes place at low temperatures (~ the uptake of CO2 on biochar by altering the surface chemistry in favor
200–300 oC) in a short period [71,72], while in hydrothermal carbon­ of CO2 adsorption, besides improving the porosity properties of the
ization, the biomass undergoes carbonization in water at high pressure biochar [4,48,82,83]. Here, microporous structure and large surface
(~ 14–22 MPa) and low temperature (~ 120–300 oC) [76,77]. Advan­ area mainly contribute to the physisorption, while surface functional
tageously, the synthesis of biochar does not require significant physical groups may primarily contribute to the chemisorption. Thus, a combi­
and/or chemical activations as those applied for the development of nation of physisorption and chemisorption advantageously improves the
activated carbon but only requires little pre- and/or post-modifications. CO2 uptake capacity of the modified biochar compared to that of pristine
The only major concern is the inability of pristine biochar to compete biochar [79,84,85].
with the commercial activated carbon due to its low porosity properties This work presents an overview of the various modification methods
and poor surface chemistry. Accordingly, a great deal of study and used to enhance the CO2 capture capacity of the nascent biochar,
investigation on the structural properties of biochar and its surface emphasizing the involved mechanisms for improving the uptake ca­
chemistry is needed to enhance its adsorption properties before it could pacity through these treatments.
be exploited at large scales.
Adsorption on biochar relies on a surface phenomenon that is highly
affected by the surface area and porosity of the biochar and its surface
functional groups. To enhance the CO2 capture capacity, various

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2. Important properties of biochar for CO2 capture diffusional activation energy [94]. The adsorption of CO2 in micropores
depends on the adsorption temperature and pressure. Ultra-micropores
2.1. Physical properties (<0.7 nm) and pores with a size of less than 1 nm are the dominant
pores responsible for the CO2 adsorption at 25 and 0 ºC, respectively. For
Gas adsorption is highly affected by the physical properties of bio­ a pressure of up to 1 bar, CO2 adsorption is governed by micropores of
char, especially the surface area and porosity. During the pyrolysis of less than 1 nm [93]. While at pressures less than 0.1 and 1 bar, CO2
biomass, high-temperature dehydration leads to the formation of pores adsorption is mostly dominated in micropores of 0.5 nm and smaller
of different categories which are nano (< 0.9 nm), micro (< 2 nm), meso than 1 nm, respectively [95]. Hence, the porosity of biochar should be
(2–50 nm), and macro (> 50 nm) pores [86]. According to a carefully controlled to obtain a high CO2 adsorption capacity. In this
meta-analysis carried out by Leng et al. [87], the surface area, total pore context, the effect of various modification techniques on the porosity
volume, micropore volume and mesopore volume of pristine biochar properties of the biochar, specifically used for CO2 capture, will be
obtained through pyrolysis are commonly distributed in the range of discussed in the following sections.
8–132 m2/g, 0.016–0.083 cm3/g, 0.012–0.060 cm3/g (with a median
value of 0.024 cm3/g) and 0.007–0.020 cm3/g (with a median value of 2.2. Chemical properties
0.009 cm3/g), respectively, as shown in Fig. 5.
The dominant factors that may affect the surface area and porosity of The surface chemistry of biochar has significant effects on the
biochar are the type of biomass or feedstock, pyrolysis condition, and adsorption of CO2; this includes the presence of various functional
used biochar modification technique (physical/chemical/physico­ groups, mineral content, surface basicity, non-polarity, and hydropho­
chemical) [87]. Depending on the type of biomass, cellulose-rich bicity. Oxygen-containing functional groups such as carboxyl, carbonyl,
biomass materials are known to produce biochar with more micro­ hydroxyl, phenolic, lactone, carboxylic acid anhydride and peroxide
pores during the pyrolysis, while pyrolysis of lignin-rich biomass feed­ groups are the important oxygen complexes that govern the reaction
stocks results in biochar with high macroporosity [86]. In addition, high mechanism in the adsorption of various adsorbates on biochar [96].
pyrolysis and activation temperature lead to a larger surface area and These O-containing functional groups usually present in biomass, but
widening of the pore size [88,89]. While for gas adsorption, micropores some are decomposed upon pyrolysis at certain temperatures, while
are highly desired, and excess widening of the pore at high pyrolysis or some functional groups can be introduced using specific activation
activation temperature would adversely affect the gas adsorption ca­ techniques [79,80,97]. Other than O-containing functional groups,
pacity of the biochar [4,48]. N-containing functional groups also highly influence the adsorption of
Specific surface area and microporosity are two interrelated prop­ CO2 [96], where the biochar with basic N-containing functional groups
erties, where generating a high volume of small micropores would forms acid-base interaction with the acidic CO2. Here, it is essential to
develop a large specific surface area, thus contributing to high CO2 control the content of specific functional groups, especially O-containing
adsorption. Multiple studies showed that a highly microporous adsor­ functional groups, because most of them are usually acidic; hence, they
bent has superior CO2 adsorption capacity [90–92]. Even the micropore are not suitable for the adsorption of CO2 with acidic character. These
volume has been reported to be far more important than total pore acidic groups include carboxylic acids, phenols, lactol and lactone
volume for CO2 adsorption, especially at ambient temperature and low groups, while pyrones, chromene and ketone belong to basic groups
pressure [93]. The presence of micropores is essential for gas adsorption although it has low basicity (Fig. 6) [96]. The acidic O-containing
because adsorption occurs in micropores due to the micropores functional groups can be easily removed during the pyrolysis of biomass,

Fig. 5. Surface area and porosity of biochar samples, pyrolyzed at the temperature range of 300–1000 oC, without additional treatment (Data were collected from the
literature). Copyright 2021 Elsevier.
Adopted with permission from [87].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 6. Acidic and basic O-containing functional groups of biochar. Copyright 2004 Elsevier.
Adapted with permission from [96].

where these functional groups undergo decomposition when the tem­ Lower contents of O and H in biochar contribute to the high hydro­
perature exceeds 100 ℃. While N-containing functional groups, such as phobicity and low polarity, which are beneficial for the adsorption of
amino groups with basic characteristics, are removed during biomass CO2; these attributes reduce the competition with the adsorption of H2O,
pyrolysis once the temperature reaches 400 oC [86]. Due to the high which is a polar molecule [103]. Besides that, lowering the ratios of
stability of the aromatic structure, the raw biochar usually preserves (O+N)/C and (O+N + S)/C, which occurs during the carbonization re­
amino groups such as pyridine in the aromatic ring structure. Like action, also enhance the hydrophobicity of biochar [104]. Here,
O-containing functional groups, for the introduction of certain N-con­ aromaticity and hydrophobicity are interrelated, where a high degree of
taining functional groups, further activation is required. aromaticity leads to a high degree of hydrophobicity. Similarly, the
The surface charge, which represents the distribution of charge on reduction of O, H, N and S as a result of carbonization makes the biochar
the surface, is dependent on the functional groups on the surface. less polar or non-polar, thus limits the adsorption of polar molecules,
Generally, the surface functional groups of biochar can be classified as which can compete with the adsorption of CO2 [103]. This applies the
(i) electron donors that contain α or π electrons such as NH2, OH, O concept of “like-dissolves-like”, where polar biochar would react with
(C–– O)R and OR and (ii) electron acceptors which contain empty or­ the polar H2O, while less polar or non-polar biochar would react with
bitals such as NO2, (C– – O)H and (C– – O)OH [98]. On this basis, various the non-polar CO2. As the two dipoles in the linear CO2 molecule cancel
acidic and basic sites are present on the outer surface and biochar pores. each other out, the CO2 molecule becomes non-polar, hence having
For example, phenols and carbonyls are weak acidic functional groups, higher interaction with the non-polar biochar than H2O and other polar
carboxyl groups are strong Brønsted acids, and pyrones and chromenes molecules; this is beneficial for the selective adsorption of CO2 over
are basic functional groups [98]. According to the reports [66,99], the competing gases on the biochar. Polarity index ((O + N)/C), which is
biochar surface is mostly charged negative which is suitable for CO2 determined by elemental analysis, is typically used as a measure to
capture. evaluate the effect of different parameters on the surface polarity [105,
Multiple studies indicated that the presence of alkali (K, Na, etc.) and 106]. For example, it has been reported with the increase of the pyrolysis
alkaline-earth metals (Ca, Mg, etc.), known as AAEM, in the biochar temperature, the polarity index of biochar decreased due to the disap­
could influence the CO2 adsorption, primarily through chemisorption pearance of polar functional groups such as -OH, COOH, C-O, as evi­
[74,78,100]. Indeed, in the presence of these elements, the basicity of denced in FTIR and XPS spectra [105].
biochar can be enhanced [101,102]. The effect of AAEM on CO2
adsorption was studied by Xu et al. [74], where various biochars with
different pH were used for CO2 capture. Among the used biomass 2.3. Methods for analyzing the physicochemical properties of biochar
feedstock, pig manure had the highest basicity (pH=10.4) compared to
wheat straw and sewage sludge, and the pig manure-derived biochar Proximate and ultimate analyses are among the most widely used
showed the highest CO2 sorption (23 mg/g), despite its smallest surface methods to determine the properties of biochar. Proximate analysis of
area. Pig manure-derived biochar had the highest mineral content, biochar is to determine its moisture, ash, fixed carbon and volatile
including K, Na, Ca and Mg, which contributed to the chemisorption of matter. Usually, high ash content is undesirable, as the inorganic min­
CO2. In another investigation, Lahijani et al. [48] showed that the eral compounds may block the pores and limit the accessibility to the
introduction of Mg, Al, Fe, Ni and Ca onto the biochar led to the adsorption sites [107]. However, Zubbri et al. [4] reported the
enhancement of CO2 capture capacity due to the basic nature of these encouraging effect of alkali content of biochar-ash, including K2O and
metals. CaO, on increasing the surface basicity and contribution to the adsorp­
tion of CO2 (with the acidic character) through carbonate formation.

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Ultimate analysis determines the elemental composition of biochar, disordered and graphitic carbon structure formed during the pyrolysis of
including C, N, H, O and S. From this analysis, the O/C, H/C and biochar [112]. NMR is normally used to analyze the aromaticity of
(O+N)/C atomic ratios can be determined, which provide insightful biochar as it is the dominant carbon structure in biochar and can
information regarding the hydrophobicity, degree of carbonization, contribute to the CO2 adsorption through the van der Waals interaction
aromaticity, and polarity of biochar [108]. Other important character­ [113]. Boehm titration can be considered as an additional character­
izations to determine the physicochemical properties of biochar include, ization with the main purpose to determine the acidic and basic func­
but not limited to, scanning electron microscopy-energy dispersive X-ray tional groups [114]. TGA analysis is used to evaluate the thermal
spectroscopy (SEM-EDX), Brunauer-Emmett-Teller (BET), Fourier stability of biochar which is an important property for the regeneration
transform infrared spectroscopy (FTIR), solid state 13C nuclear magnetic of biochar and its industrial applications [115]. Depending on the bio­
resonance (NMR), Raman spectroscopy, X-ray photoelectron spectros­ char synthesis condition and the used biochar treatment methods, re­
copy (XPS), thermogravimetric analysis (TGA) and Boehm titration as searchers usually implement a combination of these characterization
shown in Fig. 7. SEM analysis which shows the surface morphology and techniques to describe the physicochemical properties of biochar and
porosity of biochar, is usually implemented to observe the changes in the justify the possible mechanisms for CO2 adsorption.
surface morphology, pore widening/narrowing or creation of new pores
after physical or chemical activations [109]. In addition, EDX is used to 3. Possible mechanisms for CO2 capture using biochar
determine the elemental composition of biochar surface to provide
comprehensive information on the inorganic and organic chemistry of Various interactions might be involved in CO2 adsorption on biochar.
biochar surface. This is especially applicable in cases where biochar is Among the interactions, the most distinguished ones are micropore
doped with alkali metals to improve the surface basicity [109]. The filling, hydrogen bonding, van der Waals attractions, and Lewis acid-
surface area and porosity (mainly micro and mesopores) of biochar are base interactions by N- and O-containing functional groups (Fig. 8).
measured by gas adsorption, mostly N2 (77 K). BET method is then used Certainly, not all the mentioned interactions take place in CO2 adsorp­
to analyze the N2 adsorption isotherms for surface area determination, tion on any biochar, but the involved interactions are determined by the
and the total pore volume is typically calculated based on the volume of physical structure and surface chemistry of biochar.
adsorbed N2 at a relative pressure of 0.95–0.99. Dubinin-Radushkevich Studies have indicated that the physisorption of CO2 is dominated by
(DR) and t-plot are commonly adopted methods for the determination of the micropore filling effect [48,116,117]. Micropores of 0.3–0.8 nm are
micropore volume, while mesopore volume is obtained as the difference favorable for CO2 adsorption, while those below 0.5 nm are the most
between the total pore volume and the micropore volume. For the effective ones [116]. Aromatic structures in biochar can also contribute
assessment of the pore size distribution, Barrett-Joyner-Halenda (BJH) to the physical adsorption of CO2 through the van der Waals interaction
method and density functional theory (DFT) are more suitable for [116,118]. The presence of specific functional groups, particularly
mesopores and micropores, respectively [87]. FTIR and XPS are other O-containing functional groups, may lead to the interaction between
important characterization techniques used to determine the surface adsorbate and adsorbent via hydrogen bonding. As mentioned before,
functional groups. The FTIR adsorption peak and XPS binding energy are most of the O-containing functional groups are acidic; thus, in general,
helpful to quantitively and qualitatively analyze various surface func­ they would hinder the adsorption of acidic CO2 groups. However, some
tionalities, such as O- and N-containing functional groups. Here, a studies indicated that the presence of hydroxyl (-OH) and carboxyl
comparison of the characterization results obtained for fresh and spent (-COOH) in the biochar matrix might enhance the interaction with CO2
biochar (after adsorption) could explain the adsorption mechanism in molecules via hydrogen bonding [119,120]. The significant electro­
the solid-gas interface between biochar and the targeted gas, which is negativity difference between O atom (3.5) and H atom (2.1) makes the
highly dependent on the functional groups of biochar and their acidic or H atom in hydroxyl and carboxyl groups with strong electropositivity to
basic nature [110,111]. Raman spectroscopy is usually used to analyze interact with the electronegative O atom in CO2 to form a hydrogen
the carbon structure of the biochar, wherein two characteristic peaks, bond (O-H⋅⋅⋅O– – C–– O) [78,99]. This is considered a weak hydrogen
known as D-band and G-band, appear which respectively represent the bonding compared to the typical hydrogen bond between O-H⋅⋅⋅O,

Fig. 7. Most common characterization methods to analyze the physicochemical properties of biochar.

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 8. Simplified scheme of possible mechanisms involved in CO2 adsorption on biochar. Copyright 2020 Elsevier.
Adapted with permission from [116].

F-H⋅⋅⋅O, and N-H⋅⋅⋅O where this H atom is covalently bonded to highly cyanide, and pyrrole groups (Fig. 9). They have different basic strengths,
electronegative atoms, which are F, O and N atom. However, it is where pyridone, pyridine and pyrrole are known to affect the CO2
essential to note that this hydrogen bonding is only beneficial for the adsorption [122,123].
CO2 capture in the absence of H2O because of the larger dipole moment Interestingly, some of the N-containing functional groups can also
of water compared to the quadrupole moment of CO2. Hence, this develop hydrogen bonding interaction with CO2, such as pyridone and
hydrogen bonding can only participate effectively in the adsorption of pyrrole, due to the presence of the H atom next to the N atom. For Lewis
CO2 in the absence of other gases, especially water vapor [119]. acid-base interaction, the N atom possesses a lone pair of electrons and
Another mechanism that contributes to the CO2 adsorption involves thus is electron-rich; this property can facilitate the adsorption of acidic
the interaction between the basic N-containing functional groups and CO2 [122,124]. The interaction of various N-containing functional
acidic CO2 molecules, which is considered a Lewis acid-base reaction groups with CO2 was deeply discussed by Lim et al. [123] using Density
[121]. However, most of the N-containing functional groups are lost Functional Theories (DFT). They found that different N-containing
after pyrolysis reaction above 400 oC, leaving the pyridine type, which functional groups have different adsorption energies with CO2 due to
remains in the aromatic structure. Thus, chemical modifications using various interactions, such as Lewis acid-base and hydrogen bonding
N-precursors are required to introduce the basic N-containing functional interactions. Based on the study, the pyridone group possessed the
groups [86]. In principle, the common types of N-containing functional strongest adsorption energy contributed by the hydrogen bonding be­
groups are pyridone, pyridine, amine, quaternary-N, pyridine-N-oxide, tween the H atom of the hydroxyl group and the high electronegative O

Fig. 9. Structures of the N-containing functional groups modelled using DFT. Atom colors: C = gray, H = white, O = red and N = blue. Copyright 2016 Elsevier.
Adapted with permission from [123].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

atom from the CO2 molecule. Pyridine was the second one, where the biochar skeleton, the CO2 adsorption capacity increased by 15.7%. It
interaction was dominated by the Lewis acid-base reaction only. was disused that the synergistic effect was attributed to the presence of
Pyridinic-N has strong electronegativity that preferred the MgO on biochar surface that contributed to the CO2 chemisorption via
electron-deficient C atom compared to the O atom in the CO2 molecule; carbonate formation. A similar study by Zubbri et al. [4] also showed the
thus, it was feasible for CO2 adsorption. The third one was pyrrole which higher CO2 adsorption capacity of metallized biochar (76.80 mg/g) than
interacted with CO2 via hydrogen bonding, while the pyridine-N-oxide pristine biochar (68.74 mg/g), owing to the contribution of chemi­
group interacted with CO2 primarily by H-bonding (weaker than pyr­ sorption to the overall adsorption capacity, although physisorption was
idone), with smaller contribution by Lewis acid-base reaction (weaker the primary governing mechanism for adsorption as shown by kinetic
than pyridine). Other N-containing functional groups which were studies. The synergistic contribution of physisorption and chemisorption
amine, quaternary and cyanide groups formed weak Lewis acid-base was also demonstrated by Zhang et al. [79], who compared the CO2
interaction with CO2, thus are considered less significant for the CO2 adsorption capacity of CO2-NH3 treated biochar (88.89 mg/g) with CO2
adsorption. Here, the results of the theoretical study are compatible with activated biochar (76.31 mg/g), NH3 treated biochar (79.19 mg/g) and
experimental data, where previous experimental studies [122,124,125] non-modified biochar (~ 46 mg/g). They found that the CO2-NH3
showed that biochar with pyridone, pyridine and pyrrole functional treated biochar which had the highest microporosity and successfully
groups have strong interaction with CO2. In a study carried out by Fan grafted with nitrogen functional groups and was benefited from syner­
et al. [125] to develop chitosan derived N-doped microporous carbon for gistic interaction between physical and chemical adsorption showed the
CO2 capture, the major nitrogen-containing functional groups of porous highest CO2 uptake capacity among the samples. Multiple studies have
carbon were determined by XPS analysis. It was found that the dominant discussed that a high specific surface area does not guarantee a high CO2
peak was assigned to pyridone, with a minor contribution of pyridine. It uptake capacity, while the moderate surface area with high surface
was discussed that in pyridonic nitrogen, the N atom is positioned just basicity, for example, has been reported to result in high CO2 adsorption
next to the -OH group; the p orbital in -OH would form p-π conjugation [48]. In addition, the engineered biochar used for this purpose should
effect with the π bond. Hence, the N atom located in the ortho-position of present high selectivity for CO2 over other gases such as N2, H2O and air,
-OH is surrounded by a higher electron density, and consequently, its and be stable upon multiple cycles of CO2 adsorption-desorption [4].
Lewis basicity is improved. As a result, pyridone nitrogen serves as the Hence, it is necessary to tailor the porosity and the surface chemistry of
main anchor for CO2 capture. It was also discussed that pyridone and biochar to ensure the high selectivity and adsorption of CO2. Herein, the
pyrrole-like nitrogen cannot be distinguished from one another within physical, chemical and physicochemical treatments carried out to
the accuracy of XPS, and their peaks may overlap; however, since pyr­ develop engineered biochar for CO2 capture are reviewed and discussed.
idone is more stable than pyrrole at high temperature, it was more It should be noted that the discussion is focused on the modification of
plausible that the observed peak in XPS was associated with the pyr­ biochar primarily synthesized through pyrolysis, which is preferably
idone nitrogen. used to produce biochar, among the other thermochemical routes.

4. Development of engineered biochar 4.1. Physical treatment

Pristine or unmodified biochar suffers from poor textural properties, Physical treatment usually involves the thermal treatment of biochar
having low surface area and porosity [75,126]. Although various studies under an activation atmosphere or oxidizing agent, where steam and
have concluded that biochar could be an alternative for activated car­ CO2 are the most common oxidizing agents [79,116]. Activation of
bon, the CO2 adsorption capacity of biochar is not as high as activated biochar is carried out at a high temperature of above 700 oC. It can be
carbon due to its low porosity and surface area [127]. In addition, performed via two methods: (1) direct activation of biomass using an
pristine biochar possesses poor chemical surface properties, with low oxidizing agent or (2) activation of biochar using an oxidizing agent
basicity and limited functional groups [128,129]. Biochar with low after pyrolysis in an inert atmosphere. High activation temperature
surface basicity could not well interact with the Lewis acid, CO2, and the leads to the elimination of volatile matters and the development of
biochar with little functional groups would form inferior intermolecular highly porous biochar [131]. The main objective of physical activation is
forces (such as hydrogen bonding) with CO2 molecule. To enhance both to increase the internal surface area and porosity of biochar, as the
the Lewis acid-base interaction and intermolecular forces, the surface oxidizing agent penetrates across the carbon matrix at high temperature
chemistry of biochar needs to be tuned [82,83]. Therefore, tailoring the (> 700 oC) and removes some carbon atoms, thereby creates new pores
intrinsic properties of biochar and modifying its surface chemistry is and also widens the existing pores [86]. Generally, the significant
necessary to develop an “engineered biochar” with enhanced CO2 physicochemical changes during the physical treatment of biochar have
adsorption capacity and selectivity. been reported to be related to the textural characteristics, such as sur­
Engineered biochar is a term to represent modified/functionalized/ face area, pore volume and pore size. However, alterations in surface
composite biochar with enhanced CO2 adsorption capacity/selectivity chemical properties in terms of polarity, hydrophobicity and surface
compared to the pristine biochar (without physical/chemical/physico­ functional groups have been scarcely reported in previous studies [74,
chemical modifications). Engineered biochar should have physico­ 75].
chemical properties that are beneficial for the adsorption of CO2 through Activation using steam and carbon dioxide are the two well-known
physisorption and chemisorption [61]. The textural properties, such as physical modification approaches which have been used for the
large surface area and high micropore volume, significantly contribute improvement of the surface area and pore volume of pristine biochar.
to the high CO2 uptake capacity through physisorption [84,100]. Compared to chemical treatment, physical treatment using steam or CO2
Nevertheless, these are not the only factors contributing to the increased is a more convenient method for the industrial scale as it employs no
CO2 adsorption capacity. Current studies are working on the develop­ chemicals, hence is eco-friendly, reduces cost, avoids secondary pollu­
ment of engineered biochar to enhance the CO2 adsorption capacity of tion, is time-saving and produces biochar with fewer impurities [132]. A
biochar. Here, the engineered biochar must have reasonably balanced summary of the studies on enhancing the CO2 uptake capacity of biochar
textural properties (specific surface area and micropore volume) and through physical modification is provided in Table 2.
surface chemical attributes (basicity, mineral content, various func­
tional groups, non-polarity and hydrophobicity) to be benefitted from a 4.1.1. Activation using carbon dioxide
synergistic effect of physisorption and chemisorption [130]. Such syn­ Biochar activation using CO2 is one of the widely implemented
ergistic effects have been reported in different studies. For instance, physical treatments for the development of engineered biochar.
Lahijani et al. [48] showed that by incorporation of basic metal into the Compared to steam activation, CO2 activation has been claimed to be

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Table 2
A summary of previous studies on physical modification of biochar for CO2 capture.
Feedstock Biochar Physical Adsorption BET Total pore Micropore Adsorption CO2 adsorption Reference
production activation system surface volume volume temperature (◦ C) capacity (mg/g)
condition condition area (m2/ (cm3/g) (cm3/g) and pressure
g)

Almond shell Pyrolyzed at 600 CO2 at 750 ◦ C TGA 1090 0.50 na 25, 1 bar 118.83 [121]
◦
C for 2 h (2.7 mmol/g)
Olive stone Pyrolyzed at 873 CO2 at 800 ◦ C Fixed bed 909 na na 30, 1.3 bar 425.04 [133]
◦
C for 2 h column
Almond shell Pyrolyzed at 873 CO2 at 700 ◦ C Fixed bed 831 na na 30, 1.3 bar 604.56 [133]
◦
C for 2 h column
Olive stone Direct activation CO2 at 800 ◦ C TGA 1215 0.51 0.48 25, 1 bar 136.43 [80]
(3.1 mmol/g)
Almond shell Direct activation CO2 at 750 ◦ C TGA 862 0.36 0.33 25, 1 bar 118.83 [80]
(2.7 mmol/g)
Cotton stalk Pyrolyzed at 600 CO2 at 800 ◦ C Fixed bed na na 0.24 20, 1 bar ~100.00 [134]
◦
C column with
TGA
Whitewood Pyrolyzed at 500 CO2 at 890 ◦ C Fixed bed 820 0.45 na 25, 1 bar 63.00 [135]
◦
C for 100 min column
Soybean straw Pyrolyzed at 500 CO2 at 800 ◦ C Fixed bed 346 na 0.19 30, 1 bar ~75.00 [79]
◦
C for 30 min column
Whitewood Pyrolyzed at 500 Steam Fixed bed 840 0.55 na 25, 1 bar 59.00 [135]
◦
C activation at column
700 ◦ C for 1.4 h
P. nigra wood Direct activation Slow pyrolysis Surface area 217 na 0.093 25, 1 bar 49.29 [136]
using steam at analyzer (1.12 mmol/g)
700 ◦ C
Cellulose fiber Direct activation Slow pyrolysis Surface area 593 na 0.220 25, 1 bar 102.54 [136]
using steam at analyzer (2.33 mmol/g)
600 ◦ C
Date seed Pyrolyzed at 800 CO2 at 900 ◦ C Micro reaction 798 na 0.28 20, 1 bar 141.14 [137]
◦
C for 1 h calorimeter
Vine shoot Pyrolyzed at 600 CO2 at 800 ◦ C Surface area 767 0.374 0.245 25, 0.15 bar 69.53 [138]
◦
C for 1 h analyzer (1.58 mmol/g)
Palm kernel Direct activation CO2 at 950 ◦ C Static 508 0.364 0.233 25, 1 bar 110.03 [132]
shell for 60–120 min volumetric (2.5 mmol/g)
instrument
Whitewood Direct activation Steam at 700 ◦ C Single 655 0.550 na 25, 1 bar 59.00 [94]
for 1.4 h adsorption
column
Whitewood Direct activation CO2 at 700 ◦ C Single 665 0.450 25, 1 bar 63.00 [94]
for 100 min adsorption
column
Polyurethane Pyrolyzed at 400 CO2 at 900 ◦ C Surface area 206 0.10 0.08 0, 1 bar 149.63 [2]
waste ◦
C for 2 h analyzer (3.4 mmol/g)
Pine sawdust Pyrolyzed at 550 CO2 activation Surface area 581 0.25 na 25, na 32.13 [116]
◦
C at 550 ◦ C for analyzer (0.73 mmol/g)
1h
Olive mill Hydrothermal CO2 at 850 ◦ C Surface area 1135 0.476 0.373 0, 1 bar 129.61 [139]
carbonization at for 1 h analyzer (2.945 mmol/g)
350 ◦ C
Vine shoot Pyrolyzed at 600 CO2 at 800 ◦ C Surface area 536 na 0.161 25, 1 bar 117.51 [140]
◦
C for 1 h analyzer (2.67 mmol/g)
Wheat straw Pyrolyzed at 500 CO2 at 800 ◦ C Surface area 514 na 0.191 25, 1 bar 107.38 [140]
pellet ◦
C for 1 h analyzer (2.44 mmol/g)

na: not available

more beneficial to develop micropores which is much desired for CO2 area and micropore volume after CO2 activation with the values of
adsorption. In contrast, steam activation may lead to the production of 798.38 m2/g and 0.28 cm3/g, respectively, which were higher than
mesopores and macropores due to micropores widening [81]. Although those of the pristine biochar with values of 531.33 m2/g and
having a wide pore size distribution, including mesopores and micro­ 0.19 cm3/g, respectively. The CO2 activation can also promote the
pores, is favored for the adsorption of large molecules, in the case of a development of small mesopores, besides micropores formation. Here,
small molecule such as CO2, micropores, which provide a high surface micropores would be beneficial for enhancing CO2 adsorption capacity,
area, are more desired and essential [86]. Therefore, CO2 activation has while mesopores would ease the diffusion of CO2 molecules into the
a high potential to produce microporous biochar with the advantage to pores of biochar [85,140].
adsorb CO2 at ambient conditions [134]. Ogungbenro et al. [137] per­ The specific mechanism for the generation of a microporous struc­
formed CO2 activation on the seeds of date fruits, which were carbonized ture during CO2 activation is the occurrence of the char-CO2 gasifica­
at 800 ◦ C. The activation under CO2 at 900 ◦ C for one h produced tion, which is the reaction of CO2, used as the activating agent, with
modified biochar with a higher CO2 uptake capacity of 141.14 mg/g carbon (char) to produce CO (C + CO2 ↔ 2CO), also known as the
(20 ◦ C) and 129.23 mg/g (25 ◦ C) compared to that of pristine biochar, Boudouard reaction [141]. The oxygen-exchange mechanism proposed
which was 91.12 mg/g (20 ◦ C) and 83.62 mg/g (25 ◦ C). Here, the by Ergun [142] is the most widely accepted mechanism to describe this
enhanced CO2 uptake capacity was due to the improved BET surface reaction. In this reaction, CO2 is first chemisorbed on a free carbon

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

active site (Cf) and dissociated to form a reactive carbon-oxygen com­ development.
plex (C(O)) on the surface and a molecule of carbon monoxide (Eq. (1)). The effect of CO2 flow rate on the porosity properties of biochar
Then, the transfer of the reactive surface oxide from solid to gas phase could be discussed from the mass transfer point of view, where the use of
removes a carbon atom from the char and creates a new vacant active higher CO2 flow rates creates a larger concentration gradient which
site for the dissociative chemisorption of the subsequent CO2 molecule improves the bulk diffusion. Indeed, the increased driving force at
(Eq. (2)). higher flow rates compels the CO2 molecules to enter the biochar pores
at a faster rate, improving the biochar gasification rate, which increases
Cf +CO2 ↔ C(O) + CO (1)
the surface area and pore volume [106]. However, when the gas flow is
too high, due to the short residence time and insufficient contact of CO2
C(O) + C ↔ CO + Cf (2)
and carbon, the biochar gasification reaction rate is low, and conse­
This is the leading cause for the formation of microporous structures, quently, the improvement in surface area and porosity is not pro­
as hot corrosion is formed by the reaction between biochar and CO2 at nounced. Hence, a moderate CO2 flow rate of about 100–150 ml/min
high temperatures [143]. Hence, a higher CO2 activation temperature with an activation temperature above 800 oC is advocated for the CO2
would lead to a higher burn-off degree where more carbon atoms are activation of biochar [137,140,148].
being removed [144]. In fact, due to the large positive enthalpy of the Activation temperature is also known to affect the surface functional
Boudouard reaction, around 172 kJ/mol at 298 K, very high tempera­ groups of biochar. Similar to the effect of pyrolysis temperature, higher
tures (> 700 oC) are required to shift the equilibrium of the reaction to a CO2 activation temperatures also reduce the polar functional groups of
forward direction to produce CO [145]. biochar such as -OH and C– – O, hence reducing the polarity index and
Among the operating variables involved in the CO2 activation, which hydrophilicity of the biochar [105,106]. Here, -OH functional group is
are activation temperature, holding time and CO2 flow rate, previous the best example that contributes to the hydrophilicity of biochar [144].
studies have shown that activation temperature is the most dominant With the lower content of these functional groups, the biochar possesses
factor which affects the physicochemical properties, including surface low H/C and O/C ratios, thus is more hydrophobic and tends to have
area and porosity and CO2 adsorption capacity of the biochar [132,139, higher interaction with non-polar CO2 molecule and is more selective for
140]. High activation temperatures of up to 950 ◦ C intensify the porosity its adsorption, even in the presence of polar H2O molecule. Manyà et al.
and surface area of the biochar [132]. The mechanism through which [140] showed the significance of hydrophobic biochar for CO2 capture.
the porosity and surface area are improved is enhancing the endo­ The biochar samples were produced from vine shoots and wheat straw
thermic reaction between CO2 and carbon matrix at high temperatures, pellet and then physically activated using CO2 at 800 ◦ C; these samples
which consequently promotes micropore development and widens the showed a high CO2 uptake capacity of 117.51 and 107.38 mg/g,
existing pores. On the contrary, at low temperature, incomplete devo­ respectively. Both physically modified biochars was selective for CO2
latilization and less possibility of the endothermic reaction between CO2 adsorption in the presence of N2. However, the presence of H2O dras­
and carbon hinders the porosity development, especially if the activa­ tically reduced the CO2 adsorption capacity of vine shoot- and wheat
tion is conducted at a short holding time of less than 60 min. Hence, high straw pellet-derived biochars to 23.85 and 21.39 mg/g, respectively.
activation temperature is required to enable the CO2 molecules to This highlights that future studies must focus on synthesizing biochar
penetrate across the carbon matrix, react with the carbon on the active with hydrophobic properties with a reduced affinity towards water.
sites and remove carbon atoms from the char structure for pore devel­ Although the generally observed trend is that with the increase of
opment and pore size enlargement [146,147]. In a study carried out by CO2 activation temperature, the surface area and porosity of biochar
Ogungbenro et al. [137], it was observed that at the activation tem­ increase which are the prerequisites to attain a high adsorption capacity,
perature of 900 ◦ C, biochar with lower carbon content was produced however, it is worth noting that high CO2 activation temperature does
compared to that produced at 800 oC due to the burn-off effect. Based on not always produce highly microporous biochar. This is because of the
the microscope imaging, higher CO2 activation temperature developed increased reaction rate compared to the diffusion rate, which is unde­
biochar with higher porosity; however, prolonged activation time sirable for micropore formation. It is also important to have a balanced
(beyond 2 h) produced biochar with smaller surface area and lower relationship between the surface area and other properties of biochar,
microporosity. It was discussed that prolonged holding time widened such as surface functional groups, hydrophobicity, and yield. Although
the micropores, and this could continue until collapsing the pores, hence the use of high CO2 activation temperature increases the surface area
reducing the surface area and causing some sintering issues. A similar and porosity nevertheless, it reduces the surface functional groups, hy­
observation was reported by González et al. [80] who produced CO2 drophobicity, and the production yield of biochar which is an indicator
activated biochar from olive stone and almond shell. They also discussed of productivity. Achieving a high surface area and porosity at the
that excessive holding time led to the collapse of adjacent micropore expense of reducing the biochar yield, for example, might not be prac­
walls, and thus widening the micropores, along with the reduction in tical from the industrial point of view. Hence, a careful investigation and
surface area and pore volume. Rashidi et al. [132] carried out an opti­ some trade-off considerations are required to obtain biochar with opti­
mization study on the development of CO2 activated biochar produced mized structural and surface chemical properties.
from palm kernel shell, which was then used for CO2 capture. The
investigated parameters were the activation temperature (750–950 oC), 4.1.2. Activation using steam
holding time (60–120 min) and the CO2 flow rate (150–450 ml/min). Steam activation of biochar can be conducted in superheated steam
The optimum condition to obtain both a high yield of the product and a at a temperature between 700 and 900 ◦ C with a minimum activation
superior CO2 uptake capacity was determined to be the temperature of duration of 30 min, which is shorter than CO2 activation due to the
950 oC, holding time of 60 min and the CO2 flow rate of 150 ml/min at smaller size of H2O molecule that can penetrate faster into the porous
which a product yield of 61.37 wt% and a CO2 uptake capacity of carbon network [149–151]. Similar to CO2 activation, steam activation
2.49 mmol/g (109.62 mg/g) were achieved. It was discussed that at a can be conducted via two methods, which are direct activation of
high activation temperature, a short reaction time would be sufficient to biomass or activation after pyrolysis of biochar. Previous studies re­
prevent the shift of the reaction from a chemically controlled regime to a ported that steam activation could considerably enhance the surface
diffusion-controlled one. Moreover, the short reaction time will avoid porosity of biochar due to the penetration of steam through the pre­
the excessive burn-off of the biochar and would be more beneficial from cursors during the thermal activation process and the removal of carbon
the economic point of view. Yet, it should be noted that at lower reaction atoms. The general chemical reactions involved in the steam activation
temperatures, a longer residence time is required to enable the pene­ are shown in Eq. (3) and Eq. (4), which show how carbons are elimi­
tration of the CO2 molecules into the carbon matrix for pore nated and hence contribute to the larger surface area and microporosity

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

development of steam-treated biochar [48,77]. aromatic ring structure due to the penetration of H radicals across the
carbon surface [86]. Some studies showed that the formation of OH, H
C + H2 O→CO + H2 (3)
and O radicals from H2O-activation changed the carbon structure of
biochar [158,159]. These radicals, which form from the reforming of
CO + H2 O→CO2 +H2 (4)
volatiles and thermal cracking, also slow down biochar gasification by
The overall reaction between steam and carbon involves a complex occupying the reactive sites of biochar, followed by the re-arrangement
reaction, starting with the chemisorption of water, carbon gasification, of biochar structure and loss of catalytic species [88]. At temperatures
water-gas shift reaction and gasification by water, CO2 and hydrogen, as above 800 ◦ C, overreaction can occur, where the small aromatic struc­
shown in the following reactions [152]: tures are almost completely consumed, thus forming biochar with a
more ordered structure that is less reactive. These effects are more se­
C + H2 O→C(O)+H2 (5)
vere if the high temperature is accompanied by a long activation time of
C(O)→CO + C (6) more than 45 min, where the excess gasification causes the collapse of
wall structures and further widens the existing micropores, hence
CO + C(O)→CO2 + C (7) developing mesopores and macropores. This leads to a lower volume
fraction of micropores and a smaller surface area but higher ash content
CO + H2 O→CO2 +H2 (8) [131,160].
The concept of enhancement in the porosity and surface area is much
C + 2H2 O→CO2 +2H2 (9) like CO2 activation, where higher activation temperatures allow for an
efficient endothermic reaction between the steam and carbon matrix,
C + CO2 →2CO (10) enabling an adequate pore development, hence increasing the total pore
volume and surface area. Different activation temperatures influence the
C + 2H2 →CH4 (11) porosity type, where steam activation below 750 ◦ C leads to the devel­
opment of micropores while steam activation at 750 ◦ C and above may
CH4 +H2 O→CO + 3H2 (12)
result in the development of a wide distribution of micropores and
The first reaction (Eq. (5)) involves the endothermic chemisorption mesopores [131]. At higher steam activation temperatures of up to
of water (H2O) unto carbon surface, which forms surface oxide (C(O)) 850 ◦ C, the pore enlargement transforms some micropores into meso­
and may be devolved as carbon monoxide (CO) (Eq. (6)). The presence pores. However, if the high activation temperature is accompanied by a
of CO increases the rate of carbon gasification by scavenging the C(O) to holding time of longer than 45 min, pore-widening becomes dominant
produce CO2 (Eq. (7)). The reaction is then followed by the exothermic compared to the pore-deepening and new pores form, leading to a
water-gas shift reaction, where H2O is broken down into CO2 and reduction in pore volume and BET surface area [149,161]. Hence, steam
hydrogen gas (H2) (Eq. (8)). Simultaneously, carbon gasification occurs, activation requires a detailed study to determine the optimum activation
where carbon gasification by H2O produces CO2 and H2 (Eq. (9)). Here, temperature and holding time to avoid extreme pore-widening that
the presence of CO2 and H2 activates the carbon surface, where carbon might lead to a smaller surface area and lower porosity.
gasification by CO2 and H2 produces CO (Eq. (10)) and methane (CH4) Both CO2 and steam activation can introduce O-containing func­
(Eq. (11)). Then, CH4 reacts with H2O to further produce CO and H2 (Eq. tional groups on the biochar surface, which comes from the O atom of
(12)) [86,152], and the consumption of carbon contributes to the pore CO2 and steam (H2O) [162]. However, due to the smaller dimension of
development [153,154]. The porosity of biochar is also improved when H2O, steam can easily diffuse into the porous network of biochar, hence
superheated steam removes the trapped products inside the pores, which inducing a faster reaction rate and creates higher O-containing func­
were formed during the pyrolysis of biomass [155]. Fig. 10 shows an tional groups, which are mostly acidic [156]. Typically, the diversity of
example of steam-activated biochar, which experienced pore widening. O-containing functional groups found in CO2 and steam activated bio­
The pore walls of the steam-activated biochar became thinner than the char is different, where CO2 activation eliminates O-H and C– – O groups,
pristine biochar because of steam gasification. while steam activation increases COOH and phenolic functional groups
Previously, it was mentioned that CO2 activation might lead to the [163]. Since steam activation introduces O-containing functional groups
production of micropores, while steam activation may result in a such as phenolic and carboxylic groups on the biochar surface, it may
broader range of pore size distribution, where both micropores and increase the hydrophilicity and polarity of the biochar [88,164]. How­
mesopores could be created using superheated steam [156,157]. ever, the introduction of these functional groups can only be achieved at
Generally, higher steam activation temperature and treatment time low activation temperature and an extended treatment time. For the
would produce biochar with a higher volume or radius of pores and particular application of CO2 capture, higher CO2 adsorption can be
surface area [88,89]. The range of activation temperature highly in­ achieved using biochar with hydrophobic character, as this can reduce
fluences the aromatic structure, surface O-containing functional groups, competitive adsorption of H2O molecule, which usually presents in the
and AAEM species of biochar [79,80,97]. At pyrolysis temperatures of flue gas. With regards to this, high steam activation temperature (>
around 800 ◦ C, biochar has the highest content of AAEM and smaller 500 ◦ C) was reported to cause a severe loss of carboxylic and lactonic

Fig. 10. SEM images of (a) pristine and (b) steam-activated biochar derived from bamboo waste. Copyright 2014 Elsevier.
Adapted with permission from [131].

13
A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

groups (determined by Boehm titration), thus decreasing the polarity [191], who used a two-step activation using KOH and thermal activation
index of biochar [151,165]. It is known that the carboxylic group has the under N2 at 700 ◦ C to produce modified biochar (from pine sawdust)
highest affinity towards H2O molecules due to the ability of this func­ with an extremely high CO2 uptake capacity of 185.28 mg/g [191]. In
tional group to form hydrogen bonding with water [140]. The adsorbed the study, very large BET and micropore surface areas of 1728.66 and
water molecules then create clusters that can grow and coalesce to fill 1692.30 m2/g were obtained, respectively. Besides that, the total pore
more or less the pore structure of biochar. Bearing this in mind, at volume and the micropore volume were reported to be 0.697 and
increased activation temperatures where the concentration of polar and 0.671 cm3/g, respectively, which were high enough for the adsorption
O-containing functional groups reduces, the biochar surface becomes of CO2 into the microporous structure of the modified biochar. The
more hydrophobic. This is due to the lower concentration of these authors emphasized the importance of microporosity compared to the
functional groups, which serve as adsorption sites for water adsorption, surface area, where the KOH-activated biochar at 700 ◦ C showed the
and hence the biochar would become more selective towards CO2 in the highest CO2 uptake capacity although it had the lowest BET surface area
presence of water molecules. compared to the one activated at a higher temperature. It was discussed
that the higher activation temperature of 900 ◦ C created more defects,
4.2. Chemical treatment as KOH is completely transformed into potassium species (K2CO3 and
K2O) at high temperatures, hence enlarging the micropores. In addition,
Basically, chemical treatment is required to improve the surface the biochar showed selective adsorption for CO2 over N2, hence was
chemical properties of the pristine biochar, such as the surface basicity, suitable for the separation of CO2 from N2 gas [191].
surface functional groups, polarity, hydrophobicity, and aromaticity Another study with high CO2 uptake capacity was reported by Kaya
[166]. Chemical activation can be performed via two methods: (1) direct et al. [195], with a CO2 adsorption capacity of 160 mg/g. In the study,
impregnation of biomass with the chemical agent, which is further pinecone biomass was used as the precursor and carbonized at 600 ◦ C
activated by thermal treatment or (2) impregnating the pyrolyzed bio­ and further activated with KOH, followed by heat treatment at 800 ◦ C
char with the chemical agent followed by thermal treatment [53,86]. under N2. As a result, a high BET surface area and total pore volume of
Chemical treatment of biochar can be conducted by the oxidation of 1714.5 m2/g and 0.684 cm3/g were obtained, respectively. KOH acti­
biochar using basic solutions (such as potassium hydroxide (KOH), so­ vation obviously enhanced the CO2 uptake capacity of the
dium hydroxide (NaOH), etc.) [167,168], amination of biochar by the alkali-modified biochar due to enlarging the surface area and creating
introduction of amine functional groups (such as ammonia (NH3)) [82, more functional groups on the biochar surface compared to the pristine
83], and impregnation of biochar with metal oxide solution for the biochar with lower surface area (259.74 m2/g) and less basicity.
incorporation of metals with basic nature into the biochar skeleton. Alkali modification using KOH followed by thermal treatment in­
Specifically, biochar oxidation is usually carried out to create O-con­ volves consequent reduction and oxidation reactions, which lead to the
taining functional groups such as carboxyl, phenolic, hydroxyl, lactones, development of micropores and mesopores by separating and degrading
and peroxides groups on the biochar surface, while a high-temperature the graphitic layers of biochar [86]. The mechanism for the formation of
amination of biochar is typically conducted to introduce N-containing pores through KOH activation can be simplified by the following re­
functional groups. Similarly, impregnation with alkali and actions [116,139,202,203]:
alkaline-earth metals can be used to develop metallized biochar for se­
2KOH→K2 O + H2 O (13)
lective CO2 capture [86]. Overall, most of the chemical treatments
enhance the surface basicity of the biochar, hence improve the adsorp­ C + H2 O→H2 + CO (14)
tion of the acidic CO2 gas. Moreover, the addition of surface functional
groups such as amino (NH2), carboxyl (CO) and hydroxyl (OH) groups C + 4KOH→K2 O + 2H2 +K2 CO3 (15)
may create intermolecular forces such as hydrogen bonding and
dipole-dipole interaction with the CO2 molecule [118]. For the chemical K2 CO3 →K2 O + CO2 (16)
treatment, three major chemical modifications, including alkali modi­
fication, amine modification, and metal or metal oxide impregnation, 2C + K2 CO3 →2K + 3CO (17)
have been recognized as the most utilized chemical treatment ap­
proaches to improve the surface chemistry of biochar. Table 3 presents a C + K2 O→2K + CO (18)
summary of previous studies on chemically modified biochars for CO2 The reaction between carbon and KOH leads to the formation of
capture. various potassium species (K and K2CO3), CO, H2 and CO2. First, with
the temperature increase, the dehydration of KOH occurs to produce
4.2.1. Alkali-modified biochar K2O and H2O (Eq. (13)). Then, the presence of H2O induces steam
Alkali treatment of biochar using common base solutions, such as activation, which occurs at a temperature between 500 and 600 ◦ C, thus
KOH and NaOH, has received considerable interest in enhancing the releases H2 and CO as the products (Eq. (14)). KOH also reacts with the C
physicochemical properties of the pristine biochar. A literature survey surface of biochar to produce various species of potassium and H2 (Eq.
(Table 2) indicates that alkali modification using KOH is the most (15)), where the production of H2 is the highest at 500 ◦ C. When the
common chemical treatment employed to improve the physicochemical temperature reaches to above 700 ◦ C, K2CO3 is decomposed into K2O
attributes of biochar to obtain a high CO2 adsorption capacity. Here, with minor production of CO2 (Eq. (16)). Simultaneously, potassium
both physical (porosity) and chemical (surface chemistry) properties are species (K2CO3 and K2O) react with the C surface to produce a higher
modified; hence tremendous improvement in the CO2 uptake capacity is amount of metallic K and CO (Eqs. (17) and (18)), thus creating pores by
achieved compared to the physical treatment. Advantageously, base- the removal of carbon atoms. Here, at temperatures above 600 ◦ C, more
treated biochar has higher surface basicity, therefore, has a higher po­ CO are evolved until the temperature reaches 900 ◦ C [203–205].
tential for interaction with the acidic CO2 gas [200]. Moreover, the high Considering that the boiling point of potassium is 760 ◦ C, the vaporized
basicity of KOH solution causes the collapse of carbon wall structure, K at high temperatures intercalates into the carbon matrix, thus leading
hence increasing the oxygen content of biochar as the modified biochar to the expansion of the carbon atomic layers. Accordingly, for an
is functionalized with hydroxyl (OH) functional group [84,128]. effective activation, the temperature should exceed the boiling point of
Numerous studies have shown that alkali-treated biochars have a potassium to ensure its evaporation and diffusion into the carbon layers
CO2 uptake capacity of higher than 70 mg/g at ambient conditions [206]. Hence, at high activation temperatures (above 800 ◦ C), micro­
(~25 ◦ C and 1 bar), and even higher than 100 mg/g [94,116,176,178, pores development is due to the loss of C and intercalation of vaporized
191,201]. A very high CO2 uptake capacity was reported by Quan et al.

14
A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Table 3
A summary of previous studies on chemical modification of biochar for CO2 capture.
Feedstock Biochar Chemical activation Adsorption BET Total Micropore Adsorption CO2 Reference
production condition system surface pore volume temperature adsorption
condition area (m2/ volume (cm3/g) (◦ C) and total capacity (mg/
g) (cm3/g) pressure g)

Eucalyptus Direct KOH and activation under Surface area 1260 0.62 0.55 25, 1 bar 212.00 [73]
sawdust activation N2 at 600 ◦ C for 1 h analyzer (4.80 mmol/g)
African palm Pyrolyzed at KOH and activation under Surface area 1250 0.61 0.55 25, 1 bar 193.64 [169]
shell 600 ◦ C N2 at 850 ◦ C for 1 h analyzer (4.40 mmol/g)
Coal-based Direct KOH and activation under Surface area 655 0.308 0.243 25, 1 bar 107.82 [170]
activation N2 and NH3 at 600 ◦ C for analyzer (2.45 mmol/g)
2h
Cotton stalk Pyrolyzed at NH3 at 900 ◦ C for 30 min Fixed bed na na 0.17 20, na ~80.00 [84]
600 ◦ C
Soybean straw Pyrolyzed at NH3 at 800 ◦ C for 30 min Fixed bed 365 na 0.19 30, na ~80.00 [79]
500 ◦ C
Sawdust Pyrolyzed at Treated with TGA 3.17 na na 30, 1 bar 44.80 [171]
850 ◦ C monoethanolamine and
stirred for 20 min
Chicken manure Pyrolyzed at N-doped (treated with Fixed bed 301.5 0.22 0.20 20, 1 bar 446.70 [172]
700 ◦ C HNO3 solution and NH3 column (10.15 mmol/
gas at 450 ◦ C for 1 h) g)
Lignin Hydrothermal O-doped and N-doped Surface area 1788 0.91 0.49 25, 1 bar 211.25 [173]
carbonization (heat treatment with KOH analyzer (4.80 mmol/g)
and adenine at 90 ◦ C for
10 h, with activation
under N2 at 700 ◦ C for
1 h)
Walnut shell Pyrolyzed at Mg-loading (impregnation TGA 292 0.157 0.118 25, 1 bar 82.00 [48]
900 ◦ C of biochar with Mg-salt
precursor and calcined
under N2 at 500 ℃ for
15 min)
Cashew nutshell Pyrolyzed at Mixing with K2CO3 and Surface area 770 na na 25, 1 bar 273.60 [174]
500 ◦ C dried in oven at 105 ℃ for analyzer (6.22 mmol/g)
24 h
Whitewood Pyrolyzed at KOH and activation under Single 650 0.556 na 25, 1 bar 78.00 [94]
700 ◦ C N2 at 300 ℃ for 1 h adsorption
column
Bagasse Pyrolyzed at N-doped (ball milling with TGA 473 0.302 0.184 25, 1 bar 27.40 [175]
600 ◦ C NH4OH and dried in oven
at 80 ℃ for 48 h)
Hickory chip Pyrolyzed at N-doped (ball milling with TGA 548 0.356 0.215 25, 1 bar 37.40 [175]
600 ◦ C NH4OH and dried in oven
at 80 ℃ for 48 h)
Chicken manure Pyrolyzed at KOH and activation under TGA 22.22 0.052 na 25, 1 bar 76.80 [176]
400 ◦ C N2 at 700 ◦ C for 1 h
Chicken manure Pyrolyzed at HCl and activation under TGA 136.75 0.047 na 25, 1 bar 85.70 [176]
400 ◦ C N2 at 700 ◦ C for 1 h
Rambutan peel Pyrolyzed at MgO-loading TGA 504.58 0.277 0.182 25, 1 bar 75.58 [4]
900 ◦ C (impregnation of biochar
with Mg-nitrate solution
and calcination under N2
at 500 ◦ C for 15 min)
Cotton wood Pyrolyzed at AlOOH-loading (mixing of TGA 367 0.37 na 25, 1 bar 71.05 [100]
600 ◦ C biochar with AlCl3
hexahydrate in deionized
water, and pyrolyzed at
600 ◦ C under N2 for 3 h)
Black locus Pyrolyzed at KOH and activation under Surface area na 1.16 na 25, 1 bar 222.25 [177]
650 ◦ C N2 at 830 ◦ C for 1 h, and analyzer (5.05 mmol/g)
further treated with
ammonia solution
Coffee grounds Pyrolyzed at Ammoxidation (using TGA 1684 0.94 0.45 35, 1 bar 89.78 [115]
400 ◦ C APTES) and activation (2.04 mmol/g)
using KOH (heated at
400 ◦ C for 1 h and then
600 ◦ C for 1 h)
Coffee grounds Pyrolyzed at Ammoxidation (using HCl TGA 992 0.61 0.37 35, 1 bar 97.70 [115]
400 ◦ C and aniline) and (2.22 mmol/g)
activation using KOH
(heated at 400 ◦ C for 1 h
and then 600 ◦ C for 1 h)
Coffee grounds Pyrolyzed at Ammoxidation (using TGA 990 0.55 0.45 35, 1 bar 117.51 [115]
400 ◦ C melamine) and activation (2.67 mmol/g)
(continued on next page)

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Table 3 (continued )
Feedstock Biochar Chemical activation Adsorption BET Total Micropore Adsorption CO2 Reference
production condition system surface pore volume temperature adsorption
condition area (m2/ volume (cm3/g) (◦ C) and total capacity (mg/
g) (cm3/g) pressure g)

using KOH (heated at

400 ◦ C for 1 h and then
600 ◦ C for 1 h)
Rubber seed Pyrolyzed at KOH impregnation and High pressure 1129.68 0.412 25, na 43.51 [1]
shell 700 ◦ C carbonization at 700 ◦ C volumetric
for 120 min analyzer
Coconut shell Pyrolyzed at KOH and activation under Volumetric 541.8 0.29 0.194 0, 1 bar 198.05 [178]
400 ◦ C N2 at 700 ◦ C for 3 h column (4.50 mmol/g)
Rubber seed Pyrolyzed at Impregnation of biochar High pressure 480.5692 0.2635 25, 1.25 bar 99.46 [127]
shell 600 ◦ C with malic acid and volumetric
carbonized under N2 at analyzer
600 ◦ C for 1.5 h
Sawmill residue Pyrolyzed at Amine functionalization Single-bed 59.18 na 0.026 20, 1 bar ~105.62 [179]
500 ◦ C using APTES and column (2.40 mmol/g)
activation under N2 at
560 ◦ C for 2 h
Rice husk Pyrolyzed at KOH and activation under Surface area 1041 0.53 0.42 25, 1 bar 183.08 [180]
710 ◦ C N2 at 710 ◦ C for 30 min analyzer (4.16 mmol/g)
Jujun grass Hydothermal KOH and thermal Intelligent 1512 0.74 0.62 25, 1 bar 215.65 [181]
carbonization at activation under N2 at gravimetric (4.90 mmol/g)
250 ◦ C 700 ◦ C for 1 h analyzer
Camellia Hydrothermal KOH and thermal Gravimetric 1353 0.67 0.56 25, 1 bar 220.05 [181]
japonica carbonization at activation under N2 at analyzer (5.00 mmol/g)
250 ◦ C 700 ◦ C for 1 h
Rice husk Pyrolyzed at Pre-deashed by Fix bed with 451.02 na 0.219 30, 1 bar 77.90 [182]
600 ◦ C hydrofluoric acid (HF) and TGA
ammonia treatment
followed by carbonization
under N2 at 600 ◦ C for 1 h
Mesquite wood Pyrolyzed at KOH and activation under Magnetic 3167 na 1.02 25, 30 bar 1150.00 [183]
waste 450 ◦ C Ar at 800 ◦ C for 45 min suspension (26.00 mmol/
balance g)
Wheat flour Pyrolyzed at KOH and activation under Surface area 1438 0.654 0.581 25, 1 bar 153.15 [148]
700 ◦ C N2 at 700 ◦ C for 1 h analyzer (3.48 mmol/g)
Whitewood Pyrolyzed at MgO-loading Fixed bed 615 0.496 0.139 25, 1 bar 49.00 [184]
700 ◦ C (impregnation with Mg- column
nitrate solution and
calcination under N2 at
700 ◦ C)
Coconut shell Pyrolyzed at KOH and activation under Fixed bed 718 0.28 25, 1 bar 186.16 [185]
500 ◦ C N2 at 600 ◦ C for 1 h colulmn (4.23 mmol/g)
Arundo donax Pyrolyzed at Addition of chitosan and Surface area 1863 1 25, 1 bar 92.42 [186]
500 ◦ C chemical activation with analyzer (2.10 mmol/g)
ZnCl2 to produce N-doped
biochar
Arundo donax Direct KOH and activation under Surface area 1122 0.592 0.50 0, 1 bar 277.26 [187]
activation N2 at 600 ◦ C for 2 h analyzer (6.30 mmol/g)
Pomengranate Direct KOH and activation under Static 585 0.28 0.20 25, 1 bar 180.88 [92]
peel activation N2 at 700 ◦ C for 1 h volumetric (4.11 mmol/g)
analyzer
Carrot peel Direct KOH and activation under Static 1379 0.58 0.51 25, 1 bar 183.96 [92]
activation N2 at 700 ◦ C for 1 h volumetric (4.18 mmol/g)
analyzer
Fern leave Direct KOH and activation under Static 1593 0.74 0.54 25, 1 bar 181.32 [92]
activation N2 at 700 ◦ C for 1 h volumetric (4.12 mmol/g)
analyzer
Sugarcane Pyrolyzed at MgO-loading (using TGA 111.3 0.084 na 30 and 35, 235.00 [188]
bagasse 600 ◦ C MgCl2 as the precursor 1 bar
feedstock and calcination under N2
at 600 ◦ C for 3 h)
Walnut shell Pyrolyzed at N-doping (addition of urea Volumetric 4230 2.43 0.24 25, 1 bar 326.55 [189]
600 ◦ C and thermal treatment at adsorption (7.42 mmol/g)
400 ◦ C) and KOH setup
activation at 900 ◦ C under
N2 for 1 h
Vine shoot Pyrolyzed at KOH and activation under Surface area 1671 0.670 0.587 25, 0.15 bar 109.26 [138]
600 ◦ C N2 at 700 ◦ C for 1 or 3 h analyzer (2.46 mmol/g)
Peanut shell Pyrolyzed at Molten salt treatment with Gravimetric 1087 0.49 na 25, 1 bar 96.82 [190]
480 ◦ C ZnCl2, and calcination gas sorption (2.20 mmol/g)
under N2 at 480 ◦ C for analyzer
1.5 h
Sawmill residue Pyrolyzed at Fixed bed 394 na 0.16 20, 1 bar ~165.04 [179]
500 ◦ C column (3.75 mmol/g)
(continued on next page)

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Table 3 (continued )
Feedstock Biochar Chemical activation Adsorption BET Total Micropore Adsorption CO2 Reference
production condition system surface pore volume temperature adsorption
condition area (m2/ volume (cm3/g) (◦ C) and total capacity (mg/
g) (cm3/g) pressure g)

Amine functionalization-
thermal activation under
N2 at 560 ◦ C for 2 h
Pine sawdust Pyrolyzed at KOH and activation under TGA 1728 0.697 0.671 25, 1 bar 185.28 [191]
700 ◦ C N2 at 700 ◦ C for 2 h (4.21 mmol/g)
Lotus seed Pyrolyzed at KOH and activation under TGA 2230 0.96 0, 1 bar 299.27 [192]
600 ◦ C N2 at 800 ◦ C for 2 h (6.80 mmol/g)
Wood chip and Gasification KOH and activation under Surface area 1408 0.83 0.36 25, 1 bar 128.51 [193]
chicken N2 at 850 ◦ C for 2 h analyzer (2.92 mmol/g)
manure
Hickory chip Pyrolyzed at FeOOH-loading (biomass TGA na na na 25, 1 bar 160.00 [19]
600 ◦ C mixing with FeCl3.6 H2O
and pyrolysis under N2 at
600 ◦ C for 4 h)
Food waste and Gasification KOH and activation under Surface area 841.3 0.36 na 25, 1 bar 142.00 [194]
wood waste N2 at 850 ◦ C for 2 h analyzer (3.23 mmol/g)
Olive mill Hydrothermal KOH and activation under Surface area 1036 0.449 0.3544 0, 0.15 bar 143.08 [139]
carbonization at N2 at 700 ◦ C for 30 min analyzer (3.25 mmol/g)
350 ◦ C
Olive mill Hydrothermal N-doping (mixing olive Surface area 937 0.518 0.263 0, 0.15 bar 100.78 [139]
carbonization at mill waste, ZnCl2 and analyzer (2.29 mmol/g)
350 ◦ C pyrrole-2-
carboxaldehyde) and
activation under N2 at
700 ◦ C for 1 and 3 h
Pine cone Pyrolyzed at KOH and activation under TGA 1714.5 0.684 na 25, 1 bar 160.00 [195]
600 ◦ C N2 at 800 ◦ C for 1 h
Sargassum Direct KOH and activation under Fixed bed 291.8 0.24 na 25, 1 bar 46.21 [128]
seaweed activation N2 at 800 ◦ C for 2 h column (1.05 mmol/g)
Enteromorpha Direct KOH and activation under Fixed bed 26.5 0.13 na 25, 1 bar 22.89 [128]
activation N2 at 800 ◦ C for 2 h column (0.52 mmol/g)
Waste Entada Direct Base-treatment (NaOH) Fixed bed 336 0.156 0.138 50, 1 bar 84.94 [196]
Rheedii shell activation and activation under N2 at column (1.93 mmol/g)
650 ◦ C for 4 h
Waste Entada Direct Acid-treatment (HCl) and Fixed bed 488 0.196 0.180 50, 1 bar 108.26 [196]
Rheedii shell activation activation under N2 at column (2.46 mmol/g)
650 ◦ C for 4 h
Waste Entada Direct Neutral-treatment (water) Fixed bed 68 0.046 0.031 50, 1 bar 49.73 [196]
Rheedii shell activation and activation under N2 at column (1.13 mmol/g)
650 ◦ C for 4 h
Sugarcane Pyrolyzed at MgO-loading (stirring of Fixed bed 32.2 na na 25, 1 bar 174.28 [197]
feedstock 600 ◦ C MgCl2.6 H2O and column (3.96 mmol/g)
sugarcane feedstock in
deionized water and
calcination under N2 at
600 ◦ C for 2 h)
Coffee ground Pyrolyzed at MgO-loading (stirring of Fixed bed 9.8 na na 25, 1 bar 69.10 [197]
600 ◦ C MgCl2.6 H2O in deionized column (1.57 mmol/g)
water and calcination
under N2 at 600 ◦ C for
2 h)
Rice husk Pyrolyzed at MgO-loading (stirring of Fixed bed 39.5 na na 25, 1 bar 200.69 [197]
600 ◦ C MgCl2.6 H2O in deionized column (4.56 mmol/g)
water and calcination
under N2 at 600 ◦ C for
2 h)
Saw dust Pyrolyzed at MgO-loading (stirring of Fixed bed 28.4 na na 25, 1 bar 100.34 [197]
600 ◦ C MgCl2.6 H2O in deionized column (2.28 mmol/g)
water and calcination
under N2 at 600 ◦ C for
2 h)
Digestate from Pyrolyzed at N-doping (physical mixing Surface area 6.89 0.038 na na 53.69 [198]
anaerobic 600 ◦ C with urea) analyzer (1.22 mmol/g)
digestion
Sawdust Pyrolyzed at N-doping (impregnation TGA 1189 0.625 0.433 25, 1 bar 58.97 [199]
700 ◦ C of biochar with urea (1.34 mmol/g)
phosphate, and
calcination under N2 at
700 ◦ C for 2 h)

na: not available

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

K into the carbon structure [177]. Yet, it is worth noting that even biochar due to the increase of oxygen-containing functional groups, such
without thermal treatment, the porosity of biochar can be improved as hydroxyl, ketone, carbonyl, lactone, ether and alcohol [209,210].
using alkali agents, where upon the alkali impregnation of biochar and Generally, the introduction of new oxygen-containing functional groups
then its neutralization, the blocked pores are cleaned up the and the (such as C-O, C– – O, COOH, etc.) to the biochar surface due to the
inorganic matters are removed, which eventually contribute to the oxidation using oxidizing agents such as H2O2, NH3, KOH, etc. results in
porosity development [167,207]. a more negative zeta potential [211]. In a study carried out by Zhao et al.
From the previous studies, it should be noted that the amount of KOH [212], it was observed that the zeta potential of pristine biochar
and activation temperature play important roles in the improvement of increased from − 27.3 to − 32.3 mV after alkali modification using
the textural and surface properties of the modified biochar [128]. NaOH, due to exposure of basic groups on the biochar surface. Since
Generally, an excessive amount of KOH collapses the carbon wall negatively charged surfaces have indicated high selectivity towards CO2
structure, thus decreasing the BET surface area and pore volume of the [213,214], hence, it is reasonable to conclude that increase of the
modified biochar. Meanwhile, the BET surface area and pore volume are negative surface charge is beneficial for CO2 adsorption.
directly proportional to the higher activation temperature of up to
900 ◦ C [128,191,195]. As prior discussed, no chemical activation occurs 4.2.2. Amino-modified biochar
at temperatures below 400 ◦ C, and as the temperature increases to N-containing functional groups, such as pyridinic, amide, imide,
600 ◦ C, gasification of surface carbon in the presence of metal com­ lactam and pyrrolic groups, can enhance the surface basicity of biochar.
plexes occurs, and KOH begins to react with carbon, thus leading to the These functional groups could be introduced onto the biochar surface
porosity development. Furthermore, at the activation temperature of using N-containing precursors such as ammonia (NH3), amines, nitric
800 ◦ C, the intermediate products, which are K2CO3 and K2O, further acid (HNO3), melamine and polyacrylonitrile [190,215]. Surface ami­
react with the carbon, thus expanding the carbon atomic layers and nation is one of the common methods for the introduction of amino
creating new pores [208]. groups on the biochar surface and can be applied via three methods; (1)
Regarding the surface functional groups, KOH activation produces nitration using NH3, (2) nitration using amino-containing reagents such
biochar with higher phenolic, carboxylic, aromatic and alkene groups. as amines and (3) combination of the nitration and reduction reactions
However, activation temperature influences the presence of these [86].
functional groups as they are decomposed at different temperatures by In the first method, which is nitration using NH3, pre-oxidation is
the formation of CO and CO2. For the particular application of CO2 required to activate the reaction between biochar and NH3 because
capture, KOH modification was proven to increase the surface basicity of ammonia is highly reactive with carboxyl groups. For this purpose and

Fig. 11. Amination of some carboxylic acids using NH3 results in the formation of amide (II and IV), lactam (I) and imide (III and V), and further thermal treatment
leads to the formation of pyrroles (I and IV) and pyridines (II, III and V). Copyright 1994 Elsevier.
Adapted with permission from [216].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

efficient amination, pre-oxidation of biochar with nitric acid is carried electron from EDC) to produce O-acylisourea as the intermediate
out to develop carboxyl groups on the biochar surface. Next, upon the product, which is then displaced by the nucleophilic attack from amino
addition of NH3 to the biochar enriched with carboxyl groups, dehy­ groups (nucleophilic attack by HOBt on the electrophile C of activated
dration occurs (decarboxylation) to generate amide, imide (from two COOH biochar) and releases isourea as the by-product [217]. Here,
carboxyl groups) and lactam groups [134]. With further thermal treat­ HOBt is the most common additive to prevent the formation of urea. In
ment at around 200 ◦ C for 2.5 h, three reactions, which are dehydration, the second step, TEPA is reacted with the biochar, where the lone pair of
decarboxylation and decarbonylation, lead to the formation of pyrroles nitrogen from TEPA attacks the electrophilic carbon of biochar to form
and pyridines [216]. Moreover, thermal treatment leads to the decar­ amine-functionalized (amide) biochar and HOBt. Fig. 12 shows the re­
boxylation of carboxylic acid and the condensation of surface functional action involving EDC-HOBt as the activating agent and TEPA as the
groups. The overall reactions for the amination using NH3 are shown in amino-containing reagent.
Fig. 11. In the third reaction involving nitration and reduction reactions,
In the second method, low molecular weight amines, such as dieth­ electrophilic aromatic substitution can produce biochar with N-con­
anolamine (DEA) and tetraethylenepentamine (TEPA), can be used for taining functional groups on the condensed aromatic ring structure
the nitration of biochar [86]. Here, the introduction of amino groups [218,219]. Here, the nitration process is first initiated where nitro
requires the presence of OH, C– – O and COOH functional groups in the groups are introduced in the biochar structure, followed by reducing
biochar structure. In this case, the presence of epoxy in the original nitro groups to amino groups using reducing agents. First, the reaction
structure of biochar requires no pre-activation compared to carboxylic between HNO3 and sulfuric acid (H2SO4) generates nitronium ion
acid, which requires pre-activation because non-activated COOH could (NO2+) due to the protonation and slow dissociation of HNO3 (Eqs. (19)
not react with amines [82]. Hence, for an effective amination reaction, and (20)). Then, this active species (NO2+) attacks the aromatic ring of
two activating agents are used, which are 1-ethyl-3-(3-dimethylamino­ biochar forming Wheland intermediate complex (Fig. 13), followed by
propyl carbodiimide) (EDC) and hydroxybenzotriazole (HOBt). In the the deprotonation of a proton (H) to develop a nitro-aromatic com­
first step, the activation of COOH using EDC is conducted, where EDC pound. The addition of sodium dithionite (Na2S2O4) reduces the
reacts with the COOH group (abstraction of H by lone pair of the nitro-aromatic compound to anilines, and dehydration of N-containing

Fig. 12. Activation of biochar using EDC and HOBt (step 1), and amination using TEPA (step 2). Copyright 2018 Elsevier.
Adapted with permission from [82].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 13. Amination of biochar. Copyright 2014 Elsevier.

Adapted with permission from [219].

functional groups leads to the production of other possible products of about 100 ◦ C, oxidation and nitration are the two reactions that occur
[219]. during the activation of biochar with nitric acid. First, the addition of
HNO3 leads to the oxidation reaction, which occurs on the aromatic
HNO3 +H2 SO4 ↔ H2 NO+
3 +HSO4
−
(19)
rings of biochar, thus leading to ring opening and formation of two
carboxyl groups (Fig. 14). Similarly, oxidation reaction happens at the
H2 NO3 +H2 SO4 ↔ NO+ +
2 +H3 O +HSO4
−
(20)
side chain of the biochar structure to produce ester, aldehyde, and
Nitro-groups can also be introduced using an oxidizing agent such as alcohol (Fig. 15). With regards to this, higher oxygen content can be
nitric acid employing an oxidation reaction [86]. At a low temperature found in the products of oxidation reaction [220].

Fig. 14. Oxidation of aromatic compound by nitric acid [220]. Copyright 2012 Springer.

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 15. Oxidation of side chain by nitric acid [220]. Copyright 2012 Springer.

Nitration reaction then takes place after the generation of NO2+ from compared to the pristine biochar (~79.22 mg/g). Furthermore, the
two molecules of HNO3 (Eqs. (21) and (22)). modified biochar revealed a relatively stable cyclic performance, where
the CO2 adsorption capacity reduced by about 20% at the 10th cycle.
HNO3 +HNO3 →H2 NO3 + +NO3 − (21)
Here, a stable regeneration performance is important to describe the
efficiency and economical use of any adsorbent in large scale applica­
H2 NO3 + ↔ NO2 + +H2 O (22)
tions [189].
The following reaction (Fig. 11) is called electrophilic substitution Recently, some researchers have used both N-doping and KOH-
reaction because the nitro group replaces the proton (H) in the original activation for biochar modification to obtain a superior CO2 adsorp­
aromatic ring in the biochar structure. Here, NO2+ is first attached to the tion capacity. In a study conducted by Liu and Huang [115], pristine
aromatic ring, and the deprotonation (removal of H) leads to the for­ biochar was obtained by pyrolyzing the coffee ground at 400 ◦ C, then
mation of a nitro-aromatic compound (Fig. 16) [185,220]. the ammoxidation step was carried out using different amination re­
At a high temperature of up to 800 ◦ C, the oxidation level of nitric agents, and lastly, the biochar was activated with KOH by physical
acid is stronger, resulting in a higher substitution of aromatic rings by mixing (Fig. 19 (a)). Then, it was calcined under N2 at 400 ℃ for 1 h,
oxygen and thermal decomposition of the aliphatic side [222]. Hence, at and further calcined at 600 ℃ for 1 h. Three amination reagents were
high temperatures, the amount of oxygen and nitrogen in biochar in­ used for the ammoxidation of the pristine biochar: i) 3-Aminopropyltri­
creases while carbon and hydrogen decrease [223]. Excessive oxidation methoxysilane (APTES), ii) hydrochloric acid (HCl) and aniline, and iii)
thus increases the acidity of the biochar surface, as most of the O-con­ melamine. Interestingly, ammoxidation using melamine produced bio­
taining functional groups are acidic in nature [223,224]. In addition, char with the highest CO2 uptake capacity of up to 117.51 mg/g at 35 ◦ C
over-oxidation reduces the micropores and internal surface area of (Fig. 19 (b)). Based on the porosity properties, ammoxidation using
biochar due to the blockage of pore mouth by oxygen groups, hence may melamine produced biochar with the smallest BET surface area
affect the adsorption of CO2 molecules [225]. (990 m2/g) compared to the other amination reagents. Hence, it was
To enhance the CO2 uptake capacity of biochar through amine reasonable to assume that the BET surface area was not the dominant
modification, Bamdad et al. [179] synthesized N-doped biochar from factor influencing CO2 adsorption. It was discussed that the nitrogen
sawmill residues via fast pyrolysis and amine-functionalization, which content was the main factor, which affected the CO2 adsorption, where
was further activated under N2 at 560 ◦ C. They proposed a mechanism the third route produced modified biochar with the highest pyrrolic-N
for developing N-doped biochar, as shown in Fig. 17 and Fig. 18. Based content (5.1%) compared to the first and second routes. For all routes,
on the presented schemes, two steps were used, which were nitration KOH activation decreased the content of unstable N and formed
followed by reduction (first step) and condensation using APTES (second N-functional groups such as pyrrolic-N, pyridinic oxide, pyridinic-N and
step). In the first step, nitration was done by adding the biochar into the quaternary nitrogen. This chemical treatment enhanced the surface area
concentrated HCl and HNO3 solution and stirring for 50 min. Aminated and N-functional groups (dominantly pyrrolic nitrogen), resulting in a
biochar was then developed by adding sodium hydrosulfite (Na2S2O4) higher CO2 uptake capacity compared to the pristine biochar, which
under reflux condition and lastly diluted in glacial acetic acid. Then, only adsorbed 8 mg CO2 /g at 35 ◦ C. Furthermore, the modified biochar
condensation reaction was promoted by adding APTES, and lastly, was stable in cyclic CO2 adsorption-desorption up to 10 cycles with a
thermal activation was conducted under N2 at 560 ◦ C. This method reduction of only 6% (Fig. 19 (c)). It also showed higher selectivity for
introduced various functional groups, such as Si-OR, N-H, C– – O, and OH CO2 adsorption over N2 gas with a CO2/N2 selectivity ratio of 74.2
groups on the biochar surface with a high affinity for interaction with (Fig. 19 (d)). In another study conducted by Rouzitalab et al. [189],
CO2 molecules. The authors highlighted that there must be a balance N-doped biochar was synthesized from the walnut shell using urea as the
between surface functionalities and surface area. Although the applied nitrogen precursor and further activated with KOH. The introduction of
thermal activation on the N-doped biochar lowered the nitrogen content N-groups and KOH activation resulted in an adsorbent with a very high
but improved the surface area, where both properties are important for BET surface area (4230 m2/g) and micropore surface area (611 m2/g),
optimizing CO2 uptake capacity. As a result, significantly higher CO2 and a high total pore volume (2.43 cm3/g) and micropore volume
uptake capacity was obtained using the N-doped biochar (165.04 mg/g) (0.24 cm3/g). The N-doped biochar showed a superior CO2 uptake

Fig. 16. Formation of a nitro-aromatic compound by nitric acid [185,220]. Copyright 2012 Springer.

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 17. Nitration followed by reduction of biochar under reflux. Copyright 2018 American Chemical Society.
Adapted with permission from [179].

Fig. 18. Condensation of APTES under reflux at 70 ◦ C. Copyright 2018 American Chemical Society.
Adapted with permission from [179].

Fig. 19. (a) Steps for the development of modified biochar from coffee ground wastes, (b) CO2 adsorption performance of various modified biochar, (c) cyclic
performance of KMHC in CO2 adsorption-desorption and (d) selectivity study of KMHC. HC: Pristine biochar, SHC: HC ammoxidation-modified using APTES, PHC:
HC ammoxidation-modified using HCl, MHC: HC ammoxidation-modified using melamine, KSHC: SHC with KOH-modification, KPHC: PHC with KOH-modification,
KMHC: MHC with KOH-modification. Copyright 2018 Elsevier.
Adapted with permission from [115].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

capacity of 326.55 mg/g at 1 bar and 25 ◦ C and reached 617.32 mg/g directly as the precursor for the impregnation of biochar, either before
when the pressure was 10 bar. It also showed high selectivity for CO2 or after the pyrolysis of biomass. Here, two approaches can be used,
adsorption over N2 gas with a CO2/N2 selectivity of 12.70. which are dip-coating and self-assembly methods. The former involves
It should be highlighted that using different N-precursors and the mixing of biochar with a metal salt or metal oxide and stirring the
biomass would lead to various N-containing functional groups. The use suspension for several hours, followed by filtration and drying, while the
of urea phosphate was also reported to develop pores and enhance latter involves the blending of biochar with metal oxide solution and
surface basicity [199]. The mechanism lies behind the generation of leaving the suspension at a certain temperature without stirring (also
N-containing radicals, which form N-containing functional groups such known as ageing) [86]. In both approaches, multiple times rinsing using
as pyrrole, which etches the carbon surface, hence developing new pores deionized water is needed to remove the impurities and loosely bound
[226,227]. Here, reaction with additional N-containing precursors such metal oxide on the biochar surface [86]. The introduction of several
as urea phosphate releases NH3 during the pyrolysis process, where this metals, such as sodium (Na), calcium (Ca), magnesium (Mg), aluminum
NH3 is then decomposed into free radicals that eventually attack the (Al), nickel (Ni) and iron (Fe), has been reported to increase the CO2
carbon matrix and form the N-containing functional groups and possibly uptake capacity due to the enhancement of the basicity of biochar sur­
diffuse across the carbon matrix, thus developing the new pores [228]. face [48,231,232].
For the synthesis of N-doped biochar using any reagent, extreme treat­ Recently, Mg has become a material of interest for doping and
ment temperature of up to 900 ◦ C could transform some N-groups into impregnation of biochar [4,48,188]. Some studies have indicated that
aromatic N-containing species, thus reducing the N-containing func­ Mg is among the best metals to synthesize biochar composite for CO2
tional groups. This would reduce the alkalinity of the biochar surface capture. The basicity of MgO is beneficial for the adsorption of CO2 at
and consequently lower the interaction with the acidic CO2 molecule low temperatures. In the presence of MgO basic sites, a chemical inter­
[199]. As mentioned above, different feedstocks would have different action is formed between basic O2- of MgO and acidic CO2, which forms
functional groups after modification, yet the use of ammonium hy­ carbonate (CO32-) as shown in Eq. (23) [78,184,233,234]:
droxide for the modification of pristine biochar enriched with COOH
MgO + CO2 →MgCO3 (23)
would result in the formation of nitrile and amine groups in the modified
biochar [175]. To highlight, the presence of N-functional groups in­ Lahijani et al. [48] carried out a study to compare the CO2 adsorption
creases the surface basicity and polarity of the modified biochar, thus performance of different metalized biochars, prepared by metal salt
strengthening the adsorption of CO2 molecules [229]. Fig. 20 summa­ solution impregnation followed by heat treatment under N2, and found
rizes different N-containing functional groups introduced by various their activity in the order of Mg> Al> Fe> Ni> Ca> raw-biochar> Na.
amination agents. Among the samples, the highest CO2 adsorption capacity (82 mg/g) was
obtained by Mg-loaded biochar. It was discussed that the dehydration of
4.2.3. Metal or metal oxide doping Mg(NO3)2.6 H2O at around 110–190 oC (Eq. (24)), and its thermal
Metal or metal oxide can be used to modify the pristine biochar to decomposition to MgO at above 400 oC (Eq. (25)), created some active
selectively adsorb CO2 and enhance the uptake capacity of biochar. For sites (MgO) for CO2 adsorption:
this purpose, biochar can be impregnated by metal salt solutions, such as
Mg(NO3 )2 .6H2 O→Mg(NO3 )2 +6H2 O↑ (24)
aluminum chloride (AlCl3), magnesium chloride (MgCl2) and iron
chloride (FeCl3), followed by thermal treatment to convert the metal salt
Mg(NO3 )2 .6H2 O→Mg(NO3 )2 +6H2 O↑ (25)
into metal oxide [53,230]. Alternatively, metal oxide could be used

Fig. 20. Different N-containing functional groups introduced by various amination agents.

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Kinetic studies showed that the adsorption of CO2 on Mg-loaded different magnesium precursors. They used exactly 5 wt% metal solu­
biochar was mainly governed by physisorption, while MgO contrib­ tions to impregnate biochar; all samples were then subjected to calci­
uted to the chemisorption of CO2 through carbonate formation, as nation under N2 at 500 ◦ C for 15 min to create metal oxide. Results
schematically illustrated in Fig. 21 (a). They showed after metal loading, indicated that the CO2 adsorption capacity of metalized biochar was in
the BET surface area and the pore volume reduced due to some pore the following order: magnesium nitrate (76.80 mg/g)> magnesium
blockage and hence, the physisorption of CO2 decreased. Yet, after metal sulphate (70.36 mg/g) > magnesium chloride (69.76 mg/g)> magne­
loading on the biochar, the effect of chemisorption was pronounced, and sium acetate (68.15 mg/g). The adsorption capacity of magnesium ac­
the overall effect was an enhancement in the CO2 uptake capacity of etate impregnated biochar was the same as that of pristine biochar
biochar. Advantageously, the modified biochar was stable upon multiple (68.74 mg/g), and metal impregnation did not improve the CO2
cycles of CO2 adsorption-desorption with insignificant loss of CO2 up­ adsorption capacity of the biochar. It was discussed that the applied
take capacity (Fig. 21 (c)); it also showed fast CO2 desorption, which calcination temperature (500 oC) was not sufficient for the decomposi­
took less than 15 min. Moreover, the modified biochar showed consid­ tion of magnesium acetate (Mg(CH3COO)2.4 H2O), as its decomposition
erably higher selectivity for CO2 over other gases, where the modified to MgO can only occur at 650 ◦ C. While this temperature (500 ◦ C) is
biochar had a superior CO2 uptake capacity of 80 mg/g but lower uptake high enough for the decomposition of magnesium nitrate (Mg
capacity for N2 (3.24 mg/g), O2 (3.25 mg/g) and CH4 (8.75 mg/g) at (NO3)2.6 H2O) into MgO. Regarding this, some researchers favor the use
ambient condition (Fig. 21 (d)). In another recent study conducted by Xu of metal oxide as the precursor for the impregnation of biochar to avoid
et al. (2020), a synthesized biochar/Fe oxyhydroxide composite was incomplete decomposition of metal salt precursors. Studies have indi­
synthesized using a wet impregnation method. The best composite with cated that the reactivity of MgO for CO2 capture also depends on its size,
the highest content of Fe (weight ratio of 1:10 for Fe: biochar) exhibited where MgO nanoparticles possess more active sites. This is because the
a great CO2 uptake capacity of 160 mg/g at 25 ◦ C. Similar to the pre­ basic strength of O2- in the O2--Mg2+ bonds, which mostly serves as an
vious discussion on metallized biochar, physisorption was the primary adsorption site for acidic CO2, depends on its coordination and the basic
mechanism governing the CO2 adsorption on the biochar with low Fe strength of those located at the corners and edges of the crystals is higher
content (0.1%). The formation of Fe-(oxy)hydroxide increased the ba­ than those in the planes. Hence, MgO nanoparticles have more corners
sicity of the biochar, and it was found that the decomposition of Fe-(oxy) and edges due to their small size and hence have more basic O2- [78]. In
hydroxycarbonate occurred between 50 and 125 ◦ C, hence low regen­ this context, Creamer et al. [188] synthesized MgO nanoparticles and
eration temperature was required [19]. used them for the development of MgO/biochar (derived from sugar­
As mentioned, thermal treatment or calcination in an inert atmo­ cane bagasse) composite using the impregnation method, which was
sphere is required to convert metal salt into metal oxide. However, it is then heat-treated at 600 ◦ C under N2. The obtained nanocomposite
important to note that different metal salts require different calcination showed a very high CO2 uptake capacity of 235 mg/g. In another study,
temperatures. Zubbri et al. [4] developed Mg-loaded biochar using Liu et al. [78] synthesized mesoporous carbon stabilized MgO

Fig. 21. (a) Schematic illustration of the interaction between CO2 and Mg-loaded biochar synthesized using single-step pyrolysis and metal impregnation, (b)
selectivity results of Mg-loaded biochar towards CO2 over other gases and (c) cyclic performance of Mg-loaded biochar in CO2 adsorption-desorption reaction.
Copyright 2018 Elsevier.
Adapted with permission from [48].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

nanoparticles, denoted as mPC-MgO2, and used it for CO2 capture. The surface area [239]. Specifically, ultrasound treatment uses the effect of
adsorbent was synthesized through fast pyrolysis of Mg.Cl2-loaded cavitation and induces the formation of microjets following the collapse
biomass (Fig. 22 (a)), where the lignocellulosic structure of biomass was of bubbles near the solid surface. Hence, ultrasound treatment could
quickly decomposed to volatiles and bio-oil at high heating rates improve the surface area and porosity, as the cavitation effect exfoliates
((Fig. 22 (b)) and the MgCl2.6 H2O was decomposed to MgO according the structure and removes the lumps in biochar pores after pyrolysis
to the following reactions: [240–242]. The effect would thus reduce the pore blockage and, at the
same time, introduces more micropores [238]. Sajjadi et al. [238]
MgCl2 .6H2 O→MgCl2 .2H2 O + 4H2 O (26)
showed that ultrasound treatment enhanced the micropore surface area
of the sonicated biochar from 347 to 389 m2/g after sonication for 20 s.
MgCl2 .2H2 O→Mg(OH)Cl + H2 O + HCl (27)
The exposure to cavitation effect generated new pores, opened up the
Mg(OH)Cl→MgO + HCl (28) clogged pores, increased the microporosity while reducing the meso-
and macro-porosity, and even reduced the roughness of the surface
The developed mPC-MgO showed a remarkable CO2 capture capacity morphology of the sonicated biochar as a result of the exfoliation effect,
of 5.45 mol/kg (239.8 mg/g), with a superior selectivity toward CO2 which can be realized from comparing Fig. 24 (b) and (c) [238]. In
over N2 (0.045 mol/kg) and O2 (0.47 mol/kg) with respective factors of addition, more defects were introduced as deduced from Raman anal­
112 and 11 (Fig. 22 (c)). The adsorbent also revealed a stable CO2 ysis, where more transitions from sp2 to sp3 bonds occurred due to the
capture performance in 19 cycles (Fig. 22 (d)). This superb performance cavitation effect introduced by ultrasound treatment. However, the
of the synthesized adsorbent in CO2 capture was attributed to its enhancement in the surface area and porosity could only be achieved
stronger basic properties compared to the bulk MgO-based adsorbents, using a low or mild ultrasound frequency of less than 75 kHz at a
and also closely related to the porous structure of the adsorbent, where treatment duration of less than a few minutes [238,243]. While high
the dehydration (Eq. (26)) and decomposition of MgCl2.6 H2O (Eqs. (27) ultrasound frequency may lead to the structural rearrangement and
and (28)) increased the release of volatile matters during the biomass blockage of the surface sites due to the breaking down of microparticles
pyrolysis and contributed to the porosity development. It was also dis­ and lowering the microporosity of the biochar [243]. Hence, the opti­
cussed that the formed MgO might serve as an in-situ template in the mum ultrasonication frequency and time should be carefully determined
pyrolysis to develop the porous structure. to obtain an exfoliated biochar with enhanced CO2 capture capacity.
It should be highlighted that the amount of metal or metal oxide In an attempt to enhance the CO2 adsorption capacity of biochar
influences CO2 adsorption due to its effect on the specific surface area, through physicochemical modification, Chatterjee et al. [82] first
pore volume and basicity [94,197]. Most of the previous studies showed treated the biochar, derived from pine softwood, using ultrasound
that a high amount of metal or metal oxide reduces the specific surface irradiation (20 kHz for 30 s at room temperature) and then treated it
area and pore volume, and the pore blockage increases the CO2 diffusion with tetra-ethylenepentamine (TEPA) for the introduction of nitro
resistance [197]. Based on the recent studies [4,48,57,100,188], metal groups. The authors emphasized the importance of ultrasound treatment
or metal oxide-modified biochars mostly have a moderate total pore that could cause the breakage and exfoliation of biochar structure that
volume and micropore volume of less than 0.3 and 0.2 cm3/g, respec­ contain graphene oxide (GO) layers where the exfoliated GO has more
tively, which can be due to the blockage of the pores by metal or metal surface availability thus is more susceptible to chemical modification.
oxide. Specifically, narrow micropores or ultra-micropores, which have The exfoliated GO layers are rich in hydroxyl, carboxyl, and epoxy
a prominent role in CO2 adsorption at pressures less than 1 bar, are groups; thus, amines could be grafted easily on the exfoliated biochar. As
blocked by excess metal loading and the micropore diffusion resistance discussed earlier, ultrasound treatment can exfoliate the clusters of
increases [235]. On the contrary, these metals improve the surface ba­ graphitic material with various possible functional groups; hence, the
sicity of biochar which results in higher CO2 uptake. Hence, the amount exfoliated material has a higher tendency for further chemical modifi­
of metal loading should be carefully determined to balance the porosity cation. Fig. 25 schematically shows the proposed mechanism for ami­
properties and surface basicity to ensure high CO2 uptake capacity. nation of biochar, where the addition of TEPA to the ultrasound-treated
biochar induced the lone pairs of N to attack the epoxy groups of the
5. Physicochemical treatment biochar, which eventually formed the amino groups on the biochar
structure. It was explained that the presence of epoxy group on biochar
To enhance the CO2 capture performance of biochar, both physical is more beneficial than carboxyl group, which does not require any
and chemical treatments could be employed to modify the porosity, activating agent. The ultrasound-treated amine-activate biochar
surface area, and surface chemistry of the biochar. Table 4 summarizes revealed a CO2 adsorption capacity of 2.79 mmol/g (122.76 mg/g) at
the previous studies that performed some physicochemical treatments 70 oC and 0.15 atm CO2 partial pressure, which was 9 times higher than
on the biochar to improve the CO2 capture capacity. that obtained using pristine biochar.
Ultrasonication and functionalization using amine solution are In a continuing effort to develop high capacity biochar adsorbent,
among the recent advancements for the production of modified biochar. Chatterjee et al. [83] investigated the effect of different pyrolysis tem­
In this regard, Darunte et al. [237] used urea (CO(NH2)2, 6 M) and ul­ peratures (500, 600, 700 and 800 oC) prior to sono-amination of the
trasound treatment (20 s) for developing modified biochar for CO2 biochar. The biomass (miscanthus) was pyrolyzed at 700 oC and then
capture. It was found that the intensity of NH2 and OH groups on the sonicated at 20 kHz for 30 s. This biochar with high microporosity and
biochar increased, where these two functional groups are responsible for large surface area (532 m2/g) which could be easily functionalized was
the Lewis acid-base and hydrogen bonding interaction with CO2. Urea then treated with TEPA for the chemical activation. As a result of ami­
treatment for amination was found to be efficient to load N-functional nation, the percentage of N increased in the modified biochar, and the
groups onto biochar matrix and is very effective for the biochar, which is sono-aminated biochar showed high functional groups. The modified
rich in hydroxyl and carboxyl groups due to the hydrogen bond for­ biochar, which underwent sono-amination showed 3 times higher CO2
mation between biochar and the amino groups of urea (Fig. 23). adsorption capacity compared to the pristine biochar. The CO2 adsorp­
Ultrasound treatment is a recent approach that can be considered an tion capacity of the sono-aminated biochars was in the range of 2.22 and
alternative for high-temperature steam activation and could be con­ 2.89 mmol/g at 0.10 atm CO2 partial pressure and 70 oC, for biochars
ducted only at room temperature [82]. By employing the sound waves at synthesized at different pyrolysis temperatures.
a mild ultrasound frequency, the graphitic layers of biochar could be A combination of physical activation by CO2 and chemical activation
exfoliated (Fig. 24 (a)). The waves can also clean the surface and open by K2CO3 was used by Li and Xiao [236] to develop a biochar-based
up the clogged pores, developing a highly porous material with a larger adsorbent for CO2. The process involved the CO2 activation of rice

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 22. (a) Schematic representation for the synthesis of mesoporous carbon stabilized MgO nanoparticles, (b) mechanism illustration for biomass decomposition
during pyrolysis and formation of mesoporous carbon stabilized MgO nanoparticles, (c) CO2 cyclic adsorption-desorption by the mesoporous carbon stabilized MgO
nanoparticles, and (d) selectivity of mesoporous carbon stabilized MgO nanoparticles towards CO2 over other gases. Copyright 2013 American Chemical Society.
Adapted with permission from [78].

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Table 4
A summary of previous studies on the physicochemical treatment of biochar for CO2 capture.
Feedstock Biochar Physico-chemical Adsorption BET Micro- Total Micro- Adsorption CO2 adsorption Reference
production activation condition system surface pores pore pore temperature capacity (mg/g)
area surface volume volume (◦ C) and total
(m2/g) area (cm3/g) (cm3/g) pressure
(m2/g)

Cotton stalk Pyrolyzed at CO2 and NH3 at 800 ◦ C Fixed bed na 627 na 0.25 20, na ~95 [84]
600 ◦ C for 30 min column
Soybean Pyrolyzed at CO2 and NH3 at 800 ◦ C Fixed bed 491 534 na 0.21 30, na ~90 [79]
straw 500 ◦ C for 30 min column
Pine Pyrolyzed at Ultrasonication at Tubular na 261.7 na 0.09 70, 0.15 bar 122.70 [82]
softwood 600 ◦ C 20 kHz for 30 s, column CO2 in He (2.79 mmol/g)
followed by amination
using TEPA
Rice husk Pyrolyzed at 1) CO2 activation at TGA 1097 na 0.34 na 25, na 136.43 [236]
900 ◦ C 700 ◦ C for 1 h (3.1 mmol/g)
2) Impregnation with
K2CO3 under reflux
at 100 ◦ C for 1 h
Whitewood Direct steam 1) Steam activation at Single 615 na 0.496 na 25, 1 bar 49 [94]
activation 700 ◦ C adsorption
2) Impregnation with column
MgO and
calcination under
N2 at 325 ◦ C for
4 h)
Miscanthus Pyrolyzed at 1) Ultrasonication at TGA na 532 na 0.21 70, 0.10 bar 121.02 [83]
700 ◦ C 20 kHz for 30 s CO2 in He (~2.75 mmol/
2) Amination using g)
TEPA
Switchgrass Pyrolyzed at 1) Ultrasonication at TGA na 520 na 0.21 70, 0.10 bar 110.02 [83]
700 ◦ C 20 kHz for 30 s CO2 in He (~2.5 mmol/g)
2) Amination using
TEPA
Corn stover Pyrolyzed at 1) Ultrasonication at TGA na 423 na 0.20 70, 0.10 bar 102.67 [83]
700 ◦ C 20 kHz for 30 s CO2 in He (~2.333 mmol/
2) Amination using g)
TEPA
Sugarcane Pyrolyzed at 1) Ultrasonication at TGA na 352 na 0.18 70, 0.10 bar 95.37 [83]
bagasse 700 ◦ C 20 kHz for 30 s CO2 in He (2.17 mmol/g)
2) Amination using
TEPA
Wood chips Gasification KOH-treatment and Surface area 1403.9 na 0.85 0.33 25, 1 bar 60.51 [193]
and CO2 activation at analyzer (1.37 mmol/g)
chicken 550 ◦ C for 1 h
manure
Food waste Gasification KOH-treatment and Surface area 667.4 na 0.29 25, na 120.12 [116]
and wood CO2 activation at analyzer (2.73 mmol/g)
waste 550 ◦ C for 1 h
Olive mill Hydrothermal N-doping (mixing olive Gas 883 na 0.513 0.24 0, 0.15 bar 121.42 [139]
carbonization mill waste with ZnCl2 sorption (2.76 mmol/g)
at 350 ◦ C and pyrrole-2- analyzer
carboxaldehyde) and
CO2 activation at
700 ◦ C for 1 h

na: not available

Fig. 23. Hydrogen bonding between the amino group of urea and (a) H of OH group in biochar and (b) H of COOH group in biochar. Copyright 2020 Elsevier.
Adapted with permission from [238].

27
A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

Fig. 24. (a) Schematic illustration of biochar exfoliation by ultrasound waves and a better possibility of functionalization and the morphology of (b) raw biochar, (c)
sonicated biochar and (d) sonicated and amino-modified biochar. Copyright 2020 Elsevier.
Adapted with permission from [238].

Fig. 25. Mechanism of amination of biochar using TEPA. Copyright 2018 Elsevier.
Adapted with permission from [82].

husk-derived biochar at 900 ◦ C and further treating with K2CO3 solution 6. Reusability of biochar
under reflux at 100 ◦ C. The main purpose of using K2CO3 was to leach
out the ash content, as the rice husk has a high content of SiO2. Inter­ For economic purposes and large-scale applications, it is important
estingly, dual-pore structures including both micropores and mesopores to determine the regeneration ability of biochar for multi-cyclic CO2
with a high specific surface area of 1097 m2/g were developed. The adsorption-desorption. Manyà et al. [140] showed that the CO2-ac­
micropore and mesopore volumes were reported to be 0.34 cm3/g and tivated biochar produced from wheat straw pellet was stable up to 5
0.49 cm3/g, respectively. Accordingly, the modified biochar revealed a cycles of CO2 adsorption-desorption (50 and 150 oC, respectively) with a
superior CO2 uptake capacity of 136.43 mg/g at 25 ◦ C and 1 bar. In reduction of 18.2%. Another study by Quan et al. [191] showed that CO2
addition, the modified biochar was selective for CO2 over N2 with a adsorption capacity of KOH-activated pine sawdust-biochar was stable
CO2/N2 selectivity ratio of 7.6. up to 15 cycles of CO2 adsorption-desorption (50 and 200 oC, respec­
tively) with insignificant loss of CO2 capture at 50 ◦ C. In a study on
metal impregnated biochar, Lahijani et al. [48] found that the CO2
adsorption capacity of Mg-loaded biochar (from the walnut shell) was

28
A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

stable with an insignificant loss after 10 cycles at adsorption and groups also contribute to the CO2 adsorption, primarily through
regeneration temperatures of 30 and 110 ◦ C, respectively. In a similar hydrogen bonding. Besides that, the presence of AAEMs also improves
study, Zubbri et al. [11] reported the stable performance of Mg-loaded the surface basicity [74]. The hydrophobicity and non-polar nature of
biochar within 25 cycles of CO2 capture and release at the adsorption biochar are also important to avoid competition between the adsorption
temperature of 30 oC and desorption temperature of 110 oC. In another of CO2 and water. These are some of the critical factors which should be
study, Liu and Huang [115] showed that the biochar (from the coffee investigated for the development of engineered biochar.
ground) modified by amination followed by KOH-activation was stable For alkali-modified biochar, it was discussed that KOH-treated
in cyclic CO2 adsorption-desorption up to 10 cycles with a slight adsorbent has superior CO2 adsorption capacity due to the enhance­
reduction of 6%, while the adsorption and desorption were carried out at ment in its physical and chemical properties. Alkali modification of
35 and 75 ◦ C, respectively. biochar creates some improvements in the BET surface area, micropore
The regeneration ability of biochar can be inferred from the isosteric surface area and micropore volume. It was also discussed that the alkali-
heat of adsorption (Qst), which indicates the strength of the interaction modified adsorbent has higher basicity, hence provides a stronger
between adsorbate and adsorbent. Here, higher Qst is associated with the interaction with the acidic CO2 gas [191,195]. In addition, the intro­
filling of ultra-micropores, while lower Qst indicates weaker interaction duction of OH-functional groups (treated using OH-bases such as KOH
of confined CO2 in larger pores upon an increase in the surface coverage and NaOH) on the adsorbent surface contributes to the hydrogen
during CO2 adsorption [244,245]. Manyà et al. [246] compared the Qst bonding between adsorbent and CO2. Interestingly, computational ap­
of CO2-activated biochar and KOH-modified biochar obtained from vine proaches using DFT study also emphasize the importance of this inter­
shoot. It was discussed that the CO2-activated biochar exhibited a molecular force, where OH-functionalized solid sorbent shows higher
considerably lower heat of adsorption, indicating a lower energy CO2 adsorption capacity compared to the solid sorbent without func­
requirement for its regeneration. In the case of N-modified biochar, tionalization due to the introduction of hydrogen bonding [250,251].
which mostly relies on CO2 chemisorption, due to the stronger interac­ However, both experimental and DFT studies agree that the impact of
tion between N-functional groups and CO2, higher regeneration tem­ OH-functional groups on CO2 adsorption is not as high as other func­
peratures might be needed to desorb the CO2, and even some of the tional groups such as amino, cyano, thiol and nitro groups [250,251].
adsorbed CO2 may not be regenerated, which results in a loss of the For amino-modified adsorbent, experimental studies concluded that the
adsorption capacity. In a study on N-doped biochar, Rouzitalab et al. introduction of various N-containing functional groups such as pyr­
[189] showed that the loss of the CO2 adsorption capacity was insig­ idinic, amide, imide, lactam and pyrrolic highly increase the surface
nificant after 5 cycles at 25 ◦ C; however, a higher desorption tempera­ area, micropore volume and surface basicity, thus led to the stronger
ture of 150 oC was required to regenerate the adsorbent. In another interaction with CO2 molecule [82,83,179]. In terms of doping the
study, Bamdad et al. [179] observed that the CO2 adsorption capacity of biochar with metal or metal oxide, previous experimental works
N-doped biochar reduced by 20% after 10 cycles of CO2 adsorption at concluded that the introduction of AAEMs enhances the basicity of the
20 oC while the regeneration was carried out at 25 oC under vacuum. adsorbent. Most studies suggest that physisorption is the main mecha­
The FTIR analysis of the regenerated biochar and desorption test (con­ nism that governs the adsorption of CO2 on metal or metal oxide-doped
ducted in surface area analyzer) indicated a small amount of CO2 adsorbents, with a minor contribution of chemisorption by the forma­
remained on the biochar surface due to the chemisorption of CO2. This is tion of metal carbonates [4,48].
in line with the study conducted by Nguyen et al. [172], who proposed Previous experimental studies on the alkali and amino-modified
that N-modified biochar is not favorable for the multi-cycle of CO2 adsorbents indicated that through these modifications, the micropore
adsorption over 10 cycles. This may highlight the higher potential of surface area and micropore volume could be significantly improved. The
physically activated biochar for post-combustion CO2 capture. Never­ modified adsorbents also have high surface basicity with various func­
theless, more studies need to be performed to determine the strength of tional groups that lead to the stronger interaction with CO2 molecules
CO2 binding on the biochar, which is highly related to the nature of [115,189]. According to the DFT perspectives, various functional groups
N-groups. Characterizations such as FTIR and XPS analyses can be used lead to different strengths of CO2 adsorption on the adsorbents. DFT
to determine the chemical stability of the biochar upon multiple cycles studies concluded that the pyridine group has the highest CO2 adsorp­
of regeneration. tion due to Lewis acid-base interaction, followed by pyrrole and amine
due to minor Lewis acid-base interaction and major hydrogen bonding,
7. Concluding remarks and future studies and lastly followed by hydroxyl group that introduces hydrogen bonding
[250].
In this review, the mechanisms of various modification techniques For enhancing the CO2 adsorption capacity of biochar, future studies
for developing engineered biochar with enhanced CO2 adsorption ca­ may employ both alkali and amine modifications whose significant roles
pacity were deeply discussed. Based on the previous studies, both can be demonstrated both experimentally and theoretically. Through
physical and chemical properties of the engineered biochar play a role in these modifications, the physical properties in terms of surface area and
CO2 adsorption. Still, a deep study must be conducted to obtain balanced micropore volume could be increased dramatically, and the surface
properties, such as porosity and chemical surface properties, so that the chemistry of the solid sorbents could be significantly improved. Simul­
modified biochar presents high CO2 uptake capacity and be stable upon taneous use of various modifications (alkali, amino, alkali and amino
regeneration process. modifications, and doping with metal or metal oxide) may be an effi­
CO2 uptake capacity is affected by the specific surface area. Higher cient approach to obtain high CO2 adsorption capacity due to the
physisorption of CO2 is achieved by higher specific surface area due to considerable improvement in surface area and micropore volume, and
the availability of more active sites for CO2 adsorption [247]. It is also the surface chemistry. Advantageously, DFT calculations can be a
well understood that microporous structure is significant for the promising approach to reveal specific information such as the required
adsorption of gas molecules. Particularly, micropores of less than 0.8 nm compositions of alkali and N-dopants and the mechanisms that are
are beneficial for CO2 adsorption at atmospheric pressure, while mi­ involved in the modification of biochar and CO2 adsorption. For now,
cropores of less than 0.5 nm are beneficial for CO2 adsorption at low DFT studies which discuss the modification of biochar for CO2 capture
partial pressures [248,249]. For the chemical surface properties of are very scarce, probably because the structure of biochar is complex
biochar, functionalization with basic functional groups such as with various impurities.
nitrogen-containing functional groups increases the surface basicity; Previous studies have emphasized the importance of having an
hence, higher interaction with the acidic CO2 gas (Lewis acid-base optimized porosity and surface chemistry to benefit from the synergistic
interaction) is probable [190,215]. Oxygen-containing functional effect of physical and chemical CO2 adsorption. However, the

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A.N. Shafawi et al. Journal of Environmental Chemical Engineering 9 (2021) 106869

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Declaration of Competing Interest
doi.org/10.1021/ie050174v.
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