Carbon Capture Science & Technology 4 (2022) 100059

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Carbon Capture Science & Technology

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

Recent advances in biochar-based adsorbents for CO2 capture

Shifang Guo a, Yuqing Li a, Yaru Wang a, Linna Wang a, Yifei Sun b,∗, Lina Liu a,∗
a
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Nankai University, Tianjin,
300350, P.R. China
b
School of Energy and Power Engineering, Beihang University, Beijing, 100191, P.R.China

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

Keywords: The global industrialization accelerates the use of fossil fuels and hence the excessive emissions of greenhouse
Carbon capture gasses, especially carbon dioxide (CO2 ), which poses a serious threat to the ecological environment. CO2 capture
Biochar is considered as a potential strategy to reduce the amount of CO2 released into the atmosphere. The development
Modification
of adsorption materials that are both economically feasible and effective is the most critical issue. Biochar is a
Adsorption capacity
promising candidate for CO2 capture among the capture materials. It offers a diverse range of raw materials and
Long-term stability
a lower environmental impact than other adsorbent materials. Even though pristine biochar could be employed
directly to CO2 capture, it generally exhibits a poor adsorption performance. Therefore, biochar needs to be mod-
ified in practical applications to improve physicochemical properties such as specific surface area, pore structure,
and surface functional groups. This paper summaries recent research advances in biochar-based adsorbents for
CO2 adsorption. Pre-combustion capture technology and post-combustion capture technology are investigated.
The production of biochar and the influence of raw materials and process conditions on the adsorption capacity
of CO2 are described in detail. The mechanism of CO2 adsorption on biochar is also discussed, which summarized
physical and chemical adsorption, respectively, as well as the corresponding presentation of some current meth-
ods of physical/chemical modification of biochar. Finally, the future prospects are proposed in order to provide
a guideline for the adsorption of CO2 by biochar. Despite the progress made in the production of biochar for CO2
adsorption, more efforts are needed to produce biochar with higher adsorption capacity and long-term stability
for large-scale CO2 capture.

1. Introduction ment of efficient adsorbents with both superior adsorption performance

and economic feasibility is the key for the scaling up of CO2 capture
With the development of economy and the increase of human activi- technology.
ties, extensive fossil fuels are consumed, and the concentration of carbon Liquid absorbents and solid adsorbents have been extensively inves-
dioxide (CO2 ) in the atmosphere has increased year by year. In 2021, tigated in recent decades. Liquid materials were commonly used to cap-
according to the latest news from the UK Met-Office, the global con- ture carbon dioxide, such as amine liquids (Xiao et al., 2021), which
centration of CO2 in the atmosphere has reached another higher record. were widely used in industry. The advantage of liquid sorbents is that
The concentration of carbon dioxide in the Earth’s atmosphere surpasses they are more effective in capturing CO2 , but the corrosive effect of
417 ppm in February and early March this year, according to the Mauna amine liquids affects the service life of the equipment. Another draw-
Loa Observatory (MLO) in Hawaii, USA, which is nearly 50% higher back is that liquid sorbents can react chemically with other acid gasses
than the average for 1750–1800 (278 ppm) (Atmospheric 2020). CO2 is in the gas resulting in less active CO2 being absorbed. Solid adsorbents
considered as the major contributor to greenhouse gas emissions and the such as amine-supported silica (Lee et al., 2018), carbonaceous materials
main driver of climate change (Yu et al., 2008). The Intergovernmental (Kamran and Park, 2021), zeolites (Kumar et al., 2020), metal-organic
Panel on Climate Change (IPCC) notes that climate warming will bring frameworks (MOFs) (Younas et al., 2020), have gained popularity over
severe, extensive, and permanent impacts on people and ecosystems if liquid absorbents due to their higher adsorption capacity and lower cost.
the CO2 concentrations continuously grow (Köne and Büke, 2019). It However, other solid adsorbents such as MOFs and zeolites are limited
is essential to develop sustainable ways for CO2 reduction to mitigate in their application due to some of their own drawbacks. The instability
climate change. Among various CO2 reduction strategies, CO2 capture of MOFs makes them unsuitable for long-term use. If the gas contains
is a promising method for its huge abatement potential. The develop- impurities, it can even destroy the structure of MOFs. Zeolites are stable

∗
Corresponding authors.
E-mail addresses: [email protected] (Y. Sun), [email protected] (L. Liu).

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Received 10 May 2022; Received in revised form 11 July 2022; Accepted 11 July 2022
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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

and more suitable for gas adsorption, but their adsorption capacity de- trochemical, photoelectrochemical and photothermal technology which
creases rapidly once the temperature is higher than 30 °C. In addition, can transform CO2 into valuable products (Mustafa et al., 2020). After
zeolites require a high regeneration temperature so that the regenera- a certain period of time, known as its lifetime, CO2 is either perma-
tion process can consume a lot of energy (Nie et al., 2018). nently retained or released into the atmosphere. The CCU strategy is
Compared to above solid adsorbents, biochar is a kind of ma- recognized as a prominent method of mitigating human-induced carbon
terial which is insoluble, stable, highly aromatized and carbon-rich emissions.
(Y. Lee et al., 2020). The International Biochar Initiative (IBI) de- Selection of an appropriate technique for a specific CO2 capture and
fines biochar as being derived from the thermochemical combustion utilization pilot projects mainly relies on the type of fuel burning system
of biomass in an oxygen-limited environment (Lee et al., 2018). As and the amount of CO2 .
the source of biochar, biomass generally contains various waste ma- Currently there are three capture systems: i.e. pre-combustion, post-
terials from agricultural wastes, such as wood chips, peanut shells, combustion and oxyfuel combustion technologies (Osman et al., 2021).
straw and wood scraps, industrial organic waste, and urban sludge These technologies have been extensively studied, and the first two are
(Rehman et al., 2017; Martín Juárez et al., 2018; Alakoski et al., 2016; more commonly used in industrial applications. Other industrial ap-
Romero Millán et al., 2019; Li et al., 2020). Carbon, hydrogen, oxy- proaches, whether low-carbon or carbon-free, are based on one or a
gen, and nitrogen are the primary components of biochar, with car- combination of these primary methods (Kheirinik et al., 2021).
bon accounting for more than 40% of the total elements (Xue et al.,
2022). Biochar differs from traditional charcoal since biochar is in-
tended for carbon storage and environmental applications, while char- 2.1. Pre-combustion technology
coal is a charred product from biomass used as a fuel and energy source
(Steiner et al., 2010; Li et al., 2021). Biochar prepared from different The pre-combustion carbon capture technology is usually combined
raw materials and pyrolysis conditions of biomass generally exhibits with the integrated gasification combined cycle process. Powdered fossil
different physicochemical properties in terms of pore structures, spe- solid fuels, water vapor and oxygen are injected into the gasifier through
cific surface areas, surface oxygen-containing functional groups and a burner at high temperature and pressure to produce a mixture of H2 ,
elemental compositions. Consequently, it could be employed in var- CO and CO2 (40 vol.%). (Jansen et al., 2015) Then the mixture is cooled
ious aspects according to its distinct properties, such as adsorbents, and fed into a catalytic converter to produce water gas containing CO2
soil amendments, catalysts, electrode materials (Nguyen and Lee, 2016; and H2 . Pre-combustion capture is less capital intensive because it is
Mulabagal et al., 2015; Goldfarb et al., 2017; Lee et al., 2017). On ac- typically high pressure intensive and has a higher CO2 escape rate than
count of its excellent surface structure, biochar can be used as an effec- other technologies (Carminati et al., 2021). While pre-combustion tech-
tive CO2 adsorbent and a promising alternative to replace conventional nology is very effective at reducing pollution, the total cost of the plant
solid carbon-based catalysts which are economically and environmen- is usually high, and the overall performance is reduced (Olabi et al.,
tally unfriendliness (Lee et al., 2017). Currently, Many investigations 2022). Compared to other technologies, pre-combustion capture tech-
have been conducted to improve the physical and chemical properties nology has lower water consumption and can generate synthesis gas as
of raw biochar using physical and chemical processes in order to produce an alternative fuel.
modified biochar (Mian and Liu, 2020; Shafeeyan, 2010; Sizmur et al., To capture CO2 from processed syngas, carbon capture employs
2017), which can be of great help in improving the adsorption both physical and chemical methods. Chemical adsorbents, such as
capacity. carbonate and hydroxide solutions, react with the products formed
In this review, the authors summarize crucial information related to by CO2 and can highly stabilize it. Presently, n-methyl-2-pyrrolidone,
recent advances in carbon capture, biochar production techniques, and methanol, dimethyl ether of polyethylene are commercially available
emphasize on the role of biochar in the adsorption of CO2 . In carbon solvents that capture CO2 by physical adsorption (Mustafa et al., 2020).
capture, we talk about the traditional capture technologies, i.e. pre- After the separation of CO2 , hydrogen can be used as fuels for ve-
combustion capture and post-combustion capture. The production of hicles or to generate electricity through gas turbines, while the flue
biochar by pyrolysis and gasification is reviewed. Additionally, different gas is passed to heat recovery and steam power plants to generate
methods of biochar modification have been summarized to improve the electricity. Finally, CO2 is compressed and macerated before being
adsorption capacity of CO2 . In general, the development of biochar ad- transported.
sorbents for CO2 capture is still in its initial stage, whereas there exists Physical adsorbents separate adsorbed gas through pressure oscil-
a huge opportunity in the future. lation, pressure release, and gentle heating, consuming less energy
than chemical absorbents, which require more energy to break bonds
2. Recent advances in CO2 capture for regeneration. Solid adsorbents are promising alternatives to phys-
ical solvents. It has the potential to save energy while simultaneously
Carbon capture and utilization (CCU) has attracted increasing inter- reducing both capital and operating costs (Ebner and Ritter, 2009;
ests (P.D. Dissanayake et al., 2020; Jung et al., 2019). CO2 is captured Choi et al., 2009; García et al., 2011). Carbon-based materials have a
technologically from point sources or ambient air and then used in or as great potentiality for CO2 capture, especially in pre-combustion cap-
a product for commercial benefit, which is defined as CCU (de Kleijne ture where the CO2 partial pressure in the gas stream is much higher
et al., 2022). than in post-combustion flue gasses (Sun et al., 2015). Michael et al.
As shown in the Fig. 1, the first step in implementing CCU is captur- (Cox and Mokaya, 2017). produced mesoporous carbon using raw ma-
ing CO2 from industrial plants sites (hydrogen power stations, chemi- terial polypyrrole and biomass as precursors, and found that the per-
cal plants, cement plants and other fossil fuel combustion plants) and formance for pre-combustion capture and selectivity over CO2 was very
atmospheric CO2 , for which there are numerous technological alterna- superior and exceeded the benchmark MOF materials.
tives (Gao et al., 2020). The absorption of CO2 in a liquid solvent or Until now, there are two pre-combustion carbon capture technology
on a solid sorbent at low, moderate, and high temperatures, depend- plants that have reached commercial scale in operation- the Farmlands
ing on the concentration and composition of the gas stream, are the Chemical Plant located in Coffeyville, Kansas, USA, and Dakota Gasifica-
two primary separation techniques. The second stage is CO2 utilization, tion’s Great Plains Synfuels Plant in North Carolina, USA. Facilities are
which is roughly categorized into three groups: direct CO2 usage, in- capturing and separating CO2 from petroleum coke gasification or using
direct usage(carbonation, curing of cement) and CO2 conversion into coal gasification to produce synthesizers, respectively, with a maximum
value-added compounds (Salehizadeh et al., 2020). There are various annual capacity of approximately 200,000 t-CO2 per year (Olabi et al.,
conversion technologies such as thermochemical, photochemical, elec- 2022).

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Fig. 1. Scheme for carbon dioxide capture and utilization (de Kleijne et al., 2022).

2.2. Post-combustion technology sorbents for concentrated gas streams. Adsorption relies on the ability
of the gas to adsorb on the surface of the adsorbent, which can sub-
Post-combustion capture technology is relatively mature and re- sequently be regenerated by temperature or pressure oscillations and
quires only additional CO2 capture devices, which can reduce invest- has been of great research interest due to its favorable properties over
ment costs largely. Post-combustion capture technologies include, but all other alternative solutions. The adsorption process is important be-
are not limited to, chemical absorption, physical adsorption, membrane cause it’s reversible and the efficiency can be improved by functional-
separation, and low temperature distillation technologies (Kárászová izing the surface (Mukherjee et al., 2019). The viability of adsorbent
et al., 2020). applied in the factory depends on its CO selectivity, stability after mul-
At present, the method of adding chemical reagents is generally used tiple adsorptions and desorptions, and durability. The practical post-
to separate CO2 from the flue gas. The mainly commercial method is combustion capture is a thermodynamically conflicting process. On the
to use absorption liquid such as monoethanolamide for CO2 separation one hand, adsorbents can obtain a greater adsorption capacity due to
(Rochelle, 2009). The most grown-up CO2 capture technique is post- the low pressure and CO2 concentration, and on the other hand these
combustion capture via chemical absorption. Among the various sol- materials also adsorb equally large amounts of SOx and NOx , leading to
vents used in the process (amines, hot potassium carbonate, frozen am- deactivation (Mukherjee et al., 2019). Nowadays, zeolites and biochars
monia and ionic liquids, etc.), amines are considered to be by far the are popular in adsorption-based post-combustion technology, and MOF
most developed (Mac Dowell et al., 2008; Liang et al., 2015). The draw- has been investigated for larger scale applications (Akinola et al., 2022).
backs of employing amine-based solvents to absorb CO2 include that For example, Marta et al. (Plaza et al., 2016). simulated the adsorption
high concentrations of amines might corrode equipment materials, and process of biochar in a fixed bed adsorption unit with different post-
solvents do not have a large loading capacity (Liang et al., 2015). When combustion gas stream (8–30% CO2 ) compositions. Trade and Develop-
heating, the toxic gas in the flue gas is discharged, and the used solvents ment Agency (TDA) in America carried out experimental tests on the ad-
need special treatment before they can be reused. Cryogenic distillation sorption and desorption of CO2 from simulated flue gasses in coal-fired
is a process that uses low temperatures to condense, separate, and purify power plants using carbon materials modified with surface functional
CO2. It works with gas supplies that have a high CO2 partial pressure, al- groups. The four-bed vacuum swing adsorption (VSA) bench system was
lowing for direct generation of liquid CO2 for transit, storage, and use. able to achieve 95% CO2 capture and over 90 vol% CO2 product purity
However, some industrialists oppose cryogenic distillation because of (Alptekin).
the high energy consumption for refrigeration, which makes the pro- Despite the fact that adsorption-based separation technology has ma-
cess prohibitively expensive for large plants (Mukherjee et al., 2019; tured in a number of large-scale industrial applications, in the selec-
Scholes et al., 2013). Membrane separation for CO2 capture is a rela- tion and breeding of adsorbent materials, gas-solid contact systems, and
tively new application as it is straightforward and does not require any other areas, their implementation in the real post-combustion CO2 col-
chemicals or regeneration (Chao et al., 2021). It requires a certain initial lection process still confronts some obstacles (Raganati et al., 2021).
pressure and high CO2 concentration, thus the low partial pressure in
CO2 in the post-combustion flue gas needs to be addressed (Chao et al., 3. Production of biochar
2021). As well as the issue of the long-term stability of the membrane
material and its resistance to the water vapor present in the flue gas Biochemical and thermochemical pathways are viable and
will also have an impact on the practical application (Kárászová et al., well-established methods for extracting energy from biomass
2020). (Chiaramonti et al., 2003). Due to the limitation of the yield of
Capturing and separating CO2 from large volumes of combustion biochemical conversion methods, thermochemical conversion has
gasses requires a lot of energy, so it’s important to develop efficient ad- received more attention (Zhang et al., 2019). Thermochemical process

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Table 1
Operating parameters and product distribution of different biomass thermochemical processes.

Types of Reaction Heating rate( Residence time Feed size(mm) Biochar yield(%) Main products
thermochemical temperature( °C) °C/min)
process

Slow pyrolysis 400–500 5–7 >1h 5–50 25–35 Solid

(Ronsse et al., 2013)
Fast pyrolysis 850–1250 6000–12,000 <2s <1 10–25 Liquid
(Ansari et al., 2021)
Intermediate 400–650 60–600 10–30s 1–5 25–40 Liquid, solid and gas
pyrolysis
(Yang et al., 2017;
Choi et al., 2013)
Flash pyrolysis >1000 >60,000 <1s <0.5 10–25 Solid
(Cornelissen et al.,
2008)
Gasification >500 1–50 10–20s 0.2–10 5–10 Gas
(S. You et al., 2017)

can be divided into slow pyrolysis, fast pyrolysis, intermediate pyrol- (Inguanzo et al., 2002) attributed this phenomenon to the cracking re-
ysis, flash pyrolysis and gasification (Zhang and Xu, 2010)(Table 1), action that occurs when the heating temperature is lower than 650 °C,
which all produce biochar with a wide variety of physical and chem- while the decarburization reaction of oxygen-containing hydrocarbons
ical properties at different operating parameters and from different will occur when the temperature is above 650 °C. Slow pyrolysis is a po-
feedstock biomass. For instance, postponing the residence duration of tential method for producing biochar while simultaneously producing a
biochar from hours to days can result in high yield and quality biochar significant amount of bio-oil. Das (Das and Goud, 2021) used slow py-
(Wang et al., 2020). rolysis process and employed Response Surface Method (RSM) to obtain
The main raw materials for biochar production are animal manure, a maximum bio-oil yield of 35.5 wt% and with corresponding biochar
agricultural and forest residues, industrial biowaste, and marine and yield of 48 wt% at 427 °C.
aquatic organisms. Substances with low moisture content are defined
as dry biomass, such as agricultural waste straw (Leng et al., 2021; 3.1.2. Fast pyrolysis
Jayaraju et al., 2021). Whereas wet feedstock such as industrial sludge, Fast pyrolysis is a thermochemical conversion method for converting
animal manure will have a moisture content greater than 30% and there- waste or raw biomass feedstock from food crops, agriculture and forests
fore the wet feedstock will require an additional drying process. residues, municipal wastes, etc. into liquid bio-oil and small amounts
of solid products under oxygen-free environment (Hu et al., 2019). The
3.1. Pyrolysis typical conditions for fast pyrolysis are a high heating rate of more than
100 °C/min, combined with short residence time of the biomass par-
Pyrolysis is a thermochemical process that thermally decomposes or- ticles and hot vapor (0.5–2 s) at heating temperatures of 400–600 o C.
ganic materials into char, pyrolytic oil and syngas (the gaseous mixture Based on the raw material properties, pyrolysis temperature and steam
of CO, CO2 , H2 , and light hydrocarbons) under oxygen-free environment residence time in the rapid pyrolysis process, a pyrolysis liquid prod-
(Neves et al., 2011; Bridgwater et al., 2007). In Fig. 2, we can see dur- uct accounting 70–75 wt% of the original dry matter weight can be
ing the thermal decomposition process, the cellulose, hemicellulose, and obtained (Mašek, 2016). Fast pyrolysis requires raw materials with a
lignin constituting the biomass have their own set of reactions at their smaller particle size (1–2 mm) to achieve high heat transfer efficiency
respective temperatures, including cross-linking, depolymerization, and from the heat source to the biomass particles . In addition, fast pyroly-
fragmentation. The yields of pyrolysis products and the distribution of sis requires a device, which is able to control a short residence time of
carbon in the carbonaceous materials is affected by the characteristics of steam by quickly removing steam. Based on and operating conditions,
the biomass feedstock, heating temperature, heating rate and residence the percentage of pyrolysis products will also be changed accordingly.
time. (Liu et al., 2015; Bridgwater, 2012; Neves et al., 2011; Kim et al., The yield of solid char can reach 5–25%, and the gas product can reach
2018; Brewer et al., 2011; Xiong et al., 2017) Among them, slow pyrol- 10–20% (Mulabagal et al., 2015).
ysis and fast pyrolysis are most widely used, and they are distinguished
according to the heating rate. 3.1.3. Intermediate pyrolysis
Intermediate pyrolysis refers to a pyrolysis process between slow py-
3.1.1. Slow pyrolysis rolysis and fast pyrolysis. Pyrolysis conditions of 300 °C–600 °C temper-
Slow pyrolysis has a lower heating rate of 5–7 °C/min and longer ature and 2–4 s vapor residence time are usually used (X.J. Lee et al.,
residence time of more than 1 h. at the heating temperature of 300– 2020). According to previous reports, the intermediate pyrolysis has
800 °C (Liu et al., 2015). In the slow pyrolysis process, the pyrolysis the advantages of low operation temperature, the ability to process a
steam stays in the reactor and the gas phase reaction continues for a range of raw materials, and the production of high-quality products
long time, which increases the carbon yield in the pyrolysis products (Zaini et al., 2021). The intermediate pyrolysis has a good product distri-
(Mulabagal et al., 2015; Cha et al., 2016). Generally, based on the orig- bution which can produce biochar and bio-oil at the same time. Previous
inal biomass weight, the yield of biochar during slow pyrolysis pro- studies have shown that biochar obtained by intermediate pyrolysis is
cess can be up to 35–50 wt%, followed by bio-oil (Budai et al., 2014; more suitable for hydrometallurgical adsorption (Buffi et al., 2018). In
Goyal et al., 2008). Low heating rates may enable the conversion of addition, intermediate pyrolysis can effectively treat wastes with low
aromatic components in bio-oil to coke by facilitating the polymeriza- heat value and high ash content, high water content, and large volumes
tion reaction during the relatively low temperature stage of the pyroly- that cannot be processed by fast pyrolysis (Choi et al., 2013; Buffi et al.,
sis process. The yield of biochar decreases with the increase of heating 2018) (Yang et al., 2017). At present, the demand for biochar is increas-
temperature (Keiluweit et al., 2010). Previous studies have shown that ing, as well as the demand for waste utilization. Therefore, the interme-
only when the heating temperature was lower than 650 °C, the yield diate pyrolysis will be a promising solution to the conversion of solid
of biochar increased with the decrease of heating rate. Inguanzo et al. wastes to biochar.

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Fig. 2. Specific mechanisms and reaction modeling of biomass pyrolysis (reproduced from (Vamvuka, 2011).).

3.1.4. Flash pyrolysis

Flash pyrolysis is similar to fast pyrolysis, but the heating rate will
be much higher. Rapid heating rates (>1000 °C/s) and high reaction
temperatures(900–1300 °C) describe flash pyrolysis (X.J. Lee et al.,
2020; Li et al., 2013). The particle size of the biological raw materials
is smaller of about 105–250 𝜇m (Li et al., 2013). To minimize the sec-
ondary cracking, flash pyrolysis keeps a shorter residence time (<0.5 s)
than fast pyrolysis, then biomass can produce high-yield bio-oil with
a conversion efficiency of up to 70%. However, the biochar yield gets
decreased. As well as biochar in bio-oil catalyzes the polymerization re-
action in the liquid product, resulting in increased oil viscosity, high
acidity, and poor thermal stability, all of which are technical limits of
the flash pyrolysis method (Cornelissen et al., 2008).

3.2. Gasification

Gasification is a thermochemical process that uses a gasification

agent to convert carbonaceous substances into synthesis gas as the main
product, together with tar, char, and ash as the by-products. The most
commonly used gasification agents include air, oxygen, water vapor,
as well as their mixtures. During the gasification process, the main gas Fig. 3. Mechanism typically found in biomass gasification in a gasifier with air
products are CO, H2 , N2 , CO2 , etc. Although the output of gas prod- (Valderrama Rios et al., 2018).
ucts is relatively high, the production of biochar is only roughly about
5–10% of the origin biomass materials (Mohan et al., 2014; Lee et al.,
2013), which is much lower than that of pyrolysis process. It attributed sis process, such as lignin. The gas products formed during the pyrolysis
to the reason that under partial oxidation conditions, some of the carbon process include H2 , CO, CO2 , H2 O and C1– C2 hydrocarbons, while the
is converted to CO (Goyal et al., 2008). liquid product is mainly tar. During the combustion process, the residues
The mechanism of gasification can be divided into four parts: drying, in the pyrolysis stage react with oxygen to produce CO and CO2 . Then in
pyrolysis, oxidation and reduction (Ruiz et al., 2013; Yao et al., 2018; the reduction stage, remaining gasses and biochar combines with H2 O,
Blasi, 2000). Fig. 3 illustrates these stages in the gasification process us- CO2 , and H2 to generate a combination of flammable gasses (CO, H2 ,
ing air as the gasification agent. The pretreatment of biomass feedstock CO, CH4 ) and light hydrocarbons (acetylene and ethylene) (You et al.,
is usually the first step of the gasification reaction. For some raw ma- 2018).
terials with high water content, it is necessary to dry them in advance. The composition and characteristics of gas and biochar depend on
Pyrolysis occurs in the temperature range of 150∼600 °C. Components in feedstock, gasifier type, and operating conditions (temperature, pres-
biomass are decomposed to char, gas, and liquid products in the pyroly- sure, and residence time) (Cha et al., 2016). Among them, tempera-

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

ture is the most important variety that affects gasification efficiency,

gas, and biochar composition, as well as tar formation. Codignole et al.
(Codignole Luz et al., 2018). investigated the effect of various gasifica-
tion temperatures on biochar properties and discovered that remaining
biochar contains high fractions of alkali and polycyclic aromatic hydro-
carbons (PAHs) produced when temperature is high. The gasification
agent plays a crucial role on the conversion rate and the composition
of products. Soheil (Valizadeh et al., 2021) used steam and air to gasify
food wastes respectively, and found that steam gasification of biochar
results in a more compressed and less reactive char structure. In gen-
eral, gasification is an efficient thermochemical process for producing
biochar from biomass while producing combustible syngas.
When compared to pyrolytic biochar, gasification ones have lower
porosity values, which is likely due to the higher process temperature
(Qian et al., 2013).The activation of the gasification agent can partially
offset the reduction in specific surface areas and total pore volumes of
biochar. The surface area and total pore volume can be increased by
an order of magnitude after activation (Bhandari et al., 2014). In recent
years there have been a few studies on the application of gasified biochar
for CO2 capture (S. You et al., 2017; Madzaki et al., 2016; Miao et al.,
2021; Igalavithana et al., 2020). Oxygen-rich functional groups and
aromatic groups on gasified biochar can act as active sites and boost
adsorption capacity (Xue et al., 2012). Dissanayake et al. (P.D. Dis-
sanayake et al., 2020) produced biochar by gasification of wood chips
and chicken manure and obtained a certain adsorption capacity.
Fig. 4. Physical and chemical adsorption mechanism of CO2 on biomass-derived
adsorbents.

3.3. Contamination of biochar

duced in sub-optimal conditions can reduce or eliminate PAHs and VOCs
The presence of some pollutants in biochar is most likely due to con- largely (Thomas, 2021).
taminated feedstocks or the use of processing conditions that favor their
production (Kookana et al., 2011). Additionally, during the production 4. CO2 adsorption on biochar-based adsorbents
system, contaminants such as volatile organic compounds, particulates,
polycyclic aromatic hydrocarbons and heavy metals may taint biochar Biochar has recently been used in considerable research to develop
(Wang et al., 2019; De la Rosa et al., 2019; Kuśmierz et al., 2016). Un- new carbon adsorbents for use due to its porous structure and the pres-
der some circumstances, biochars can introduce organic and inorganic ence of basic functional groups. The conversion of biomass to biochar
contaminants into the environment. through pyrolysis thermochemical process, instead of burned directly
For example, the concentration of PAHs is shown to be strongly im- or mineralized by microorganisms, results in lower CO2 emissions. Ni-
pacted by feedstock type, production temperature, and residence du- trogen (N), sulfur (S) or phosphorus (P) heteroatoms and some inor-
ration. Biochar produced by slow pyrolysis has a lower PAH content ganic materials in organic structures are among the biomass feedstocks
(De la Rosa et al., 2019; Wang et al., 2017). The possible reason is that (Wang and Wang, 2019). Furthermore, biochar can be produced from
PAHs are released to gas during slow pyrolysis because of the longer abundant biomass wastes, so it is regarded as an economically fea-
residence time. And PAHs is easier to be concentrated on biochar dur- sible and environmentally friendly material for capturing CO2 . How-
ing fast pyrolysis or gasification (Hilber et al., 2017). Regarding volatile ever, the use of biochar on a large scale is hampered by the fact that
organic compounds (VOCs), the pyrolysis of biomass produces vapors, pristine biochar is limited by its low porosity and poor surface chem-
which then condense to produce high concentrations of VOCs in the istry to achieve the adsorption capacity of commercial activated carbon
biochar (Buss and Mašek, 2014; Buss and Mašek, 2016). In general, (Shafawi et al., 2021; Serafin et al., 2021). In particular, the physisorp-
proper pyrolysis unit design and feedstock evaluation can reduce the tion between biochar and CO2 is mainly dependent on the pore structure
content of PAHs, VOCs, dioxins, and persistent free radicals (PFRs) for and surface area, while the surface functional groups are mainly depen-
safe biochar production (Han et al., 2022).When the feedstock contains dent on the Lewis acid-base interaction in chemisorption (Serafin et al.,
minimal heavy metals, the achieved biochar also consists of less heavy 2017; Deng et al., 2014). Therefore, there is a need for the present exten-
metals, suggesting that the selection of appropriate feedstock is a pre- sive research and investigation into the structural properties of biochar
requisite to ensure the safe application of biochar. If researchers choose and its surface chemistry, so that modified biochar with enhanced ad-
proper biomass feedstocks and also proper biochar production process sorption capacity can be obtained at a lower cost (Fig. 4).
conditions, the environmental risk of contaminants in biochar can be
considered low and the contaminants should not hinder the large-scale 4.1. CO2 physisorption on biochar
application of biochar (Han et al., 2022). Not only that, it is also nec-
essary to monitor the concentrations of pollutants in biochar after pro- The mechanism of CO2 capture by biochar and many solid adsor-
duction and before application. bents depends mostly on physical adsorption (Lahijani et al., 2018;
Various strategies have been proposed by researchers to mitigate the Chia et al., 2015). Various biochars with varying surface areas and
formation of contaminants and obtain purified biochar, such as remov- pore structures have been investigated and used for CO2 adsorption by
ing PAHs by drying biochar thermally at 100 °C, 200 °C and 300 °C, effectively utilizing their physical properties (Mahmoud et al., 2015;
where the maximum PAHs content can be reduced by 88.1% at 100 °C Park et al., 2016; Ding et al., 2016; Mubarak et al., 2013).
(Kołtowski and Oleszczuk, 2015). Heat treatment at 200 °C or pretreat- When biomass is pyrolyzed, dehydration and the release of volatile
ment for rinsing can significantly reduce the VOCs concentration in the constituents from the carbon matrix form biochar pores and rudimen-
biochar. In general, aging and thermal post-treatment of biochars pro- tary pores (Bagreev et al., 2001). According to the pore size classifica-

6
S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

tion of the International Union of Pure and Applied Chemistry(IUPAC), from H2 O molecules, biochar with hydrophobic and non-polar proper-
pores with diameters greater than 50 nm are classified as macroporous, ties might improve CO2 adsorption. Several studies have revealed that
those with diameters between 2 and 50 nm as mesopores, and those with the CO2 adsorption capacity of biochar may be lessened under humid
diameters less than 2 nm as micropores (Everett, 1972). Biochar’s CO2 environment because of high affinity for H2 O of most porous materials
capture capacity depends on micropores less than 1 nm in diameters (Nugent et al., 2013; Gao et al., 2015). The high H/C and O/C ratios indi-
(Y. Li et al., 2022), because narrow micropores are close to the dynamic cate a converse degree of aromaticity and carbon fixation (S. You et al.,
diameter of CO2 molecule and have a stronger attraction to CO2 due 2017). Acid-base interaction of N and O-containing functional groups
to overlapping adsorption forces and potential fields from neighboring on biochar with CO2 is the most significant chemisorption interactions
pore walls (Guo et al., 2016). Macropores enhance CO2 diffusion to re- (Shafawi et al., 2021). The effect of chemical properties such as alkali
duce pressure drop, mesopores provide a passageway for mass transfer metals and nitrogen-, sulfur- and oxygen-containing surface functional
at the gas-solid interface, and micropores form the packing space for groups on biochar on CO2 adsorption is mainly introduced.
CO2 adsorption (Shen and Fan, 2013). Physical adsorption can be en-
hanced by adjusting the pore distribution of biochar: containing lots 4.2.1. Alkali and alkaline earth metals
of micropores, appropriate mesopores, and small macropores with high Biomass is composed of carbon, hydrogen, oxygen, sulfur, nitrogen,
specific surface area to produce biochar with multi-stage porous struc- and small amounts of other elements, including alkali metals, alka-
tures (Chen et al., 2017). Angin (Angın, 2013) et al. found that micro- line earth metals, and heavy metals, depending on the type or type of
pores contributed less to adsorption capacity at high temperatures, and biomass (Gezae Daful et al., 2022). Alkali elements and alkaline earth
that pore volume and micropores of biochar decreased at elevated tem- metals (Ca, Mg, K, Na, etc.) can enhance the alkalinity of biochar, and
peratures above 500 °C. It attributed to the fact that at high temperatures in turn increases the affinity for acidic CO2 , manifesting itself in the
it is no longer micropores that dominate, but the phenomenon of pore enhanced adsorption capacity for CO2 (Walton et al., 2006; Yuan et al.,
widening and coalescence of adjacent pores, with a reduction in pore 2011). And these unique properties of biochar can facilitate the chemical
volume. adsorption of acid CO2 to form carbonates, bicarbonates, carbonates, or
Specific surface area and microporosity are interrelated, where the minerals. CO2 chemisorption via chemical reactions between absorbents
generation of many small micropores will result in a large specific sur- and CO2 is available on metal oxides and amine containing materi-
face area. The larger surface area provides more active sites for CO2 als. Through zwitterion mechanisms, two amine functional groups on
adsorption through physical adsorption. Brunauer-Emmett-Teller (BET) biochar can chemically combine with one CO2 molecular, yielding car-
is the most common method used to calculate the surface area of porous bamate and ammonia pairs (Choi et al., 2009; D’Alessandro et al., 2010;
materials based on nitrogen or argon adsorption isotherms. Huang et al. Rashidi and Yusup, 2016).
(Huang et al., 2015). pyrolyzed rice straw by microwaves to produce Xu et al. (Xu et al., 2016) produced biochar from pig manure, sewage
biochar for CO2 adsorption. They reported that the specific surface area sludge and wheat straw for CO2 adsorption. The alkali metals and al-
was the most important characteristic of biochar in CO2 adsorption. Pre- kaline earth metals on the surface of three biomasses were different,
vious studies suggested that adsorbents with a large surface area could while chemisorption was closely related to the minerals in the biochar.
have a high CO2 capture capacity. Mukherjee (Mukherjee et al., 2021) Xu suggestd that the sorption of CO2 all started with the dissolution
used coffee grounds to produce biochar and captured captures CO2 at of CO2 in an aqueous film on the surface of the biochar, followed by
30–90 °C at a constant CO2 concentration. The maximum adsorption ca- gradual dissociation into HCO (Köne and Büke, 2019– and CO3 2– , fol-
pacity of 2.8 mmol/g was obtained for a BET surface area of 539 m2 /g lowed by reaction with the mineralogical components of the biochar to
of biochar. The adsorption kinetics of coffee grounds biochar followed a form carbonate, bicarbonate or subcarbonate products. It was claimed
pseudo-first-order kinetic model and had a low activation energy, and it that chemical adsorption possibly plays a major role in CO2 adsorption
reflects the adsorption’s physical nature (Zhang et al., 2014). However, (K. Li et al., 2022).
when the char surface area was large enough, the quantity of nitroge-
nous groups played a more important role in the adsorption of CO2 on 4.2.2. Surface functional groups
the biochar surface. The surface area of biochar rises with increasing Different raw materials and pyrolysis conditions determine whether
pyrolysis temperature and residence time, which is owing to the pro- the resulting biochar is rich in functional groups. Basic functional groups
duction of volatiles that can increase pore volume (Ahmad et al., 2014). on the surface are divided according to their electronegativity into elec-
During modification of biochar using different compounds, the volume tron donors (OH, NH2 , OR or (C = O)R groups) formed by the presence of
and surface area of the micropores increased initially with increasing electrons and electron acceptors ((C = O)OH, (C = O)H or NO2 ) formed
the temperature, which was reduced as the temperature was raised to by the presence of empty orbitals (Lehmann and Joseph, 2012). Func-
more than 800 °C (Xiong et al., 2013; Zhang et al., 2016). Francisco tional groups containing O, N, S and P on biochar are currently being
(Lopez-Tenllado et al., 2021) et al. compared the physical adsorption studied for their effect on CO2 adsorption capacity. Basic surface func-
of carbon dioxide after modification of biochar with ball milling with tional groups play a crucial role in the CO2 adsorption of biochar due
unground biochar and found that ball milling led to an increase in pore to surface basicity, which enhance the affinity of the biochar to CO2
volume and surface area of biochar. The adsorption capacity would be (Shafeeyan, 2010).
limited by the surface properties.
4.2.2.1. Oxygen-containing functional groups. Pyrones, chromenes and
4.2. CO2 chemisorption on biochar ketones of the oxygen-containing functional groups are basic groups
that contribute to the alkalinity of the surface. However, most oxygen-
The surface chemistry of biochar also has a significant impact containing functional groups are acidic, including carboxylic acids,
on CO2 adsorption, such as alkali and alkaline earth metals (AAEM) phenols, lactones and lactone groups (Montes-Morán et al., 2004;
(Lahijani et al., 2018), different surface functional groups (Liu et al., Chiang and Juang, 2017), which are not conducive to the adsorption
2019), alkalinity, hydrophobicity, non-polarity (Shafawi et al., 2021) of acidic CO2 molecules from an acid-base reaction point of view. How-
and aromaticity (Igalavithana, 2020). The CO2 adsorption capacity of ever, it is also believed that the introduction of oxygen atoms into the
biochar can be enhanced by increasing the alkalinity of the biochar sur- carbon surface to form acidic oxygen-containing functional groups fa-
face (Walton et al., 2006; Yuan et al., 2011), changing the surface func- cilitates hydrogen bonding interactions between the carbon surface and
tional groups to improve the interaction with CO2 , or decreasing the O CO2 molecules, particularly carboxyl and hydroxyl groups. Carboxyl and
and H content of the biochar, contributing to high hydrophobicity and hydroxyl groups increase the polarity of the adsorbent and facilitate
low polarity (P.D. Dissanayake et al., 2020). By restricting competition the adsorption of CO2 with the quadrupole moment (Xing et al., 2014;

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Table 2
Types of different functional groups of biochar and CO2 adsorption capacity.

Biomass materials Modification Funtional groups Adsorption Adsorption References

methods conditions capacity(mmol/g)

sugarcane bagasse – NH2 25 °C, 1bar 1.67 (Creamer et al.,

and hickory wood 2014)
coffee grounds (1)introduce 0.5 g Pyrrolic-N 35 °C, 1bar 2.67 (Liu and
melamine in the Huang, 2018)
solutionand
hydrothermal at
160◦ C for
24h(2)KOH
activation at 400◦ C
for 1h
highly oxidized add poly(sodium S–O, S = O, 30 °C, 1bar 3.2 (Seredych et al.,
graphite oxide 4-styrene sulfonate) C–S–C/R–S2 –OR, 2016)
R2 S=O/R–SO2 –R,
R–SO3 H/SO4 2– ,
RO2 –S–S–R/–SO3 H
cotton stalks CO2 –ammonia 20 °C, 1bar 2.26 (Zhang et al., 2014)
modification at
800◦ C
cotton stalks ammonia 20 °C, 1bar 2.25 (Xiong et al., 2013)
modification at amides,pyridine,C = N
700◦ C
sawdust treat with mo- amine groups, 30 °C, 1bar 1.02 (Madzaki et al.,
noethanolamine(MEA) phenolic groups, 2016)
and stir for 20 min ketone
pine sawdust and steam activation for C–O, N-containing 25 °C, 1bar 0.73 (Igalavithana, 2020)
paper mill sludge 45 min at 550◦ C functional groups
rice husk deashing N = O, pyridine 30 °C, 1bar 1.77 (Zhang et al., 2015)
pretreatment(mix C = N, C–N
HF,water and raw
material) at 60◦ C for
24h
bagasse and hickory balling milling with NH2 , C≡N 25 °C, 1bar 0.85 (Xu et al., 2019)
chips ammonium
hydroxide
resin spheres treat with S–O, S≡O, –SO3H, 25 °C, 1bar 4.28 (Sun et al., 2018)
concentrated sulfuric sulfoxide
acid at 180 °C for 2h
poplar sawdust add C-S, SO, thiophene 25 °C, 1bar 3.82 (Guo et al., 2021)
sulfur-containing
waste liquid and sitr
for 2h
hexagonally packed Add acids (H2 SO4) to Thiophene, sulfone 25 °C, 1bar 3.60 (Li et al., 2016)
mesoporous silica catalyze the
polymerization
reactions and obtain
S-doped porous
carbons
human hair – pyridinic N, 0 °C, 1bar 5.50 (Zhao et al., 2015)
pyrrolic/pyridonic
N, and quaternary N
coconut shell (1)add glucosamine N–O, N–H, C–N, 30 °C, 1bar 4.23 (Yaumi et al., 2017)
and carbonized C≡N
(2)activated by KOH

Kudin et al., 2008; Song et al., 2020). Liu et al. (Liu and Wilcox, 2012) milling, and the nitrogen functional group species doped onto the sur-
concluded that the oxygen-containing functional groups increased CO2 face of the biochar were mainly amine (-NH2 ) and nitrile (C≡N). The
adsorbed in the microporous structure because the higher electron den- nitrogen-doped biochar showed a 31.6%−55.2% higher adsorption ca-
sity around the oxygen-containing functional groups attracts more CO2 . pacity of CO2 than pristine biochar, due to the strong pole-pole inter-
action between the large quadrupole moment of the carbon dioxide
4.2.2.2. Nitrogen-containing functional groups. Experts have proposed molecule and the polar sites associated with the nitrogen functional
various nitrogen-containing functional groups on the surface by re- (Xu et al., 2019).
acting the biochar with nitrogen-containing reagents or activating
the biochar with nitrogen-containing prerequisites. Common nitrogen- 4.2.2.3. Sulfur-containing functional groups. Compared to nitrogen-
containing functional groups (amide, imine, pyridine, pyrrole, and lac- containing functional groups, sulfur-containing functional groups have
tam groups) promote the growth of alkalinity on the surface of biochar yet to be investigated in relation to CO2 adsorption (Saha and Kien-
(Shafeeyan, 2010; Shen and Fan, 2013; Guo et al., 2018) (Table 2). Ni- baum, 2019). Some researchers suggest that the presence of sulfur-
trogen functional groups can also contribute to enhance interactions containing functional groups such as sulphonic acid, sulphoxide, sul-
between carbon surfaces and acid molecules, such as dipole-dipole, phone and thiophene on biochar can increase the alkalinity and sur-
H-bonding, and covalent bonding and so on (Shen et al., 2010). Xu face polarity of biochar, and therefore enhancing the adsorption of CO2
et al. obtained nitrogen-doped biochar using ammonium hydroxide ball through acid-base interactions and polar interactions (Saha et al., 2017;

8
S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Seema et al., 2014). Several researchers have analyzed the adsorption

energy as supporting evidence for the effect of sulfur functionality in
CO2 adsorption. Xia et al. (Xia et al., 2012). calculated that the CO2 ad-
sorption energy (Qst) of carbon with sulfur-containing functional groups
was as high as 59 kJ/mol, indicating a strong interaction between CO2
molecules and S-doped carbon pore walls. Li et al. (Li et al., 2017). used
calculations using density-functional theory (DFT) to demonstrate that
S-doping can increase the adsorption energy between CO2 molecules
and the S-graphene surface.
In recent years, some investigations have been conducted on ni-
trogen and sulfur co-doped biochar materials for CO2 capture. The
co-doped biochar adsorbents all exhibit good CO2 adsorption proper-
ties, fast CO2 adsorption kinetics, and moderate heat of adsorption
(Zhao et al., 2015; Lu et al., 2021; Ma et al., 2022; Shi et al., 2019;
Shao et al., 2022), but not much research has been done on the adsorp-
tion mechanisms of nitrogen and sulfur functional groups. The current
study is expected to provide new insights into the mechanism of CO2
adsorption on heteroatom-doped biochar.
Fig. 5. CO2 adsorption isotherms at 25 °C. WFW20: biochars with a composition
4.3. Effects of process conditions on CO2 adsorption of 20% of food waste/80% of wood, WFW30: biochars with a composition of
30% of food waste + 70% of wood, WFW40: a composition of 40% of food
Biochar structure and physio-chemical properties alter due to differ- waste + 60% of wood, WFW40-K: a composition of 40% of food waste + 60% of
ences in structure and composition of diverse biomass feedstocks and wood+ KOH, WFW40-KC: a composition of 40% of food waste + 60% of wood
pyrolysis conditions (Bridgwater, 2012; Budai et al., 2014; S. You et al., +KOH + CO2 (Igalavithana et al., 2020).
2017; Antal et al., 2000; Bourke et al., 2007). Assessing the impact of
operating parameters on biochar adsorption capacity, such as pyroly-
sis and gasification conditions, is critical for designing and controlling
biochar properties.

4.3.1. Effect of feedstocks

There is a variation in the CO2 adsorption capacity of biochar pro-
duced from different raw materials. Creamer et al. (Creamer et al.,
2014). employed biochar produced from the co-pyrolysis of sugarcane
bagasse (BG) and hickory wood (HW) to the adsorption of CO2 at 25
o C. Biochar produced with larger surface areas showed a higher CO
2
adsorption capacity (73.55 mg/g at 25 o C). More active sites for CO2 ad-
sorption are provided with a higher surface area, leading to a greater ad-
sorption capacity (Creamer and Gao, 2016). Serafin et al. (Serafin et al.,
2017) found that biochars produced from carrot peels at 700 °C showed
CO2 adsorption capacities of 4.18 mol/kg at 25 °C. Xu et al. (Xu et al.,
2016)produced biochars from sewage sludge, pig manure, and wheat
Fig. 6. CO2 adsorption capacities of both raw and sono-chemically ac-
straw with the CO2 adsorption capacities of 0.41, 0.53, and 0.78 mol/kg
tivated biochar samples synthesized at different pyrolysis temperatures
respectively at 25 °C. Igalavithana et al.99 produced biochar from feed- (Chatterjee et al., 2020).
stock mixtures of food waste and wood waste in different proportions. In
Fig. 5, it revealed that when wood wastes occupies the highest propor-
tion, the biochar owned the strongest CO2 adsorption capacity, while a biomass pyrolysis (Patra et al., 2021). Although the nitrogen content de-
higher proportion of food wastes in the raw material was detrimental creased with increasing temperature, the carbon content increased sig-
to CO2 adsorption. Feedstock types influenced the biochar chemical and nificantly, thus contributing to the improvement in CO2 adsorption ca-
physical characteristics, and the high percentage of hetero atoms (N and pacity. However, further increasing the pyrolysis temperature to 800 °C
S) on the surface contributed to high CO2 adsorption. If a large-scale ap- decreased the adsorption capacity values greatly compared to that ob-
plication of biomass adsorbents for CO2 capture is desired, it requires tained at 700 °C. This could be attributed to the decrease in nitrogen
the development of more biomass feedstocks and techno-economic anal- content and the destruction of surface porosity at higher temperature
ysis. (800 °C). As a result, choosing an appropriate pyrolysis temperature in-
volves a tradeoff between the surface and chemical qualities discussed
4.3.2. Effect of temperature above.
Similar with feedstock types, the structural and compositional fea-
tures of biochar, such as surface area, pore morphologies, surface 4.3.3. Effect of heating rate
functional groups, and elemental compositions, are also affected by Biochar yield is significantly affected by heating rate. The increase
the pyrolysis temperature. (Tag et al., 2016) For example, Chatterjee of heating rate led to a decrease in the yields of biochar (Angın, 2013).
(Chatterjee et al., 2020) et al. investigated the influence of pyrolysis Pyrolysis products and volatile organic matter have enough time to
temperature (500, 600, 700, 800 °C) on the properties and CO2 adsorp- diffuse from the biochar particles when the heating rate of the process
tion capacities of biochar derived from herbaceous and agro-industrial is low. Low heating rates support the retention of structural complexity,
feedstocks. The adsorption capacity of all biochars increased gradually whereas high heating rates result in the loss of structural complexity
as the temperature increased from 500 °C to 600 °C (Fig. 6). This is due to local melting of cell structures, phase transitions, and swelling
because biochar produced in low temperature has a poor porous struc- (Leng and Huang, 2018). When biomass gasification was used to pro-
ture, low specific surface area, and is easily blocked by tar formed during duce biochar, with the increase of heating rate, although the carbon con-

9
S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

version rate decreased, the gasification reactivity was improved, then of unactivated biochar. Furthermore, gas purging speeds up the ther-
the gasification rate increased (Tian et al., 2021). It cannot be deduced mal breakdown of carbonaceous materials and improves the aromatic-
that a higher heating rate of such biomass would imply a higher CO2 ad- ity. (Igalavithana et al., 2018). And the synthesized carbon materials
sorption, since the pore size must be within a certain range to effectively produced synthetically should be of purity after CO2 activation, so there
adsorb CO2 . Previous studies suggested that adsorbents with a large sur- is no need for a washing stage after the activation process (Rashidi and
face area could have a high CO2 capture capacity. Low heating rates are Yusup, 2016).
usually preferable in terms of biochar output yield and stability, despite Steam activation is another typical modification method for aid-
the fact that they take longer. ing devolatilization and the development of a crystalline phase as well
as removing contaminants such as incomplete combustion products
4.3.4. Effect of residence time Rajapaksha et al., 2016). Steam gasification of biochar is typically car-
Pathomrotsakun et al. investigated the effect of process parameters ried out at temperatures ranging from 500 to 850 °C, with treatment
including residence time (30, 45, 60 min) on fuel properties of biochar, times ranging from 1 to 7 h (Xie et al., 2022). During the modification
and found that residence time only slightly affected fuel properties process, oxygen from water molecules is exchanged to the free active
of biochar (Amenaghawon et al., 2021). Zhao (B. Zhao et al., 2018) centers on the carbon surface(Eq. (1)), while the hydrogen produced
et al. found that residence time in the range of 10–100 min only had combines with the carbon on the surface of the biochar to form sur-
a minimal effect on rapeseed stem biochar yield. In a short residence face hydrogen complexes. (Eq. (2)-(3) Consequently, thus incomplete
time, a near optimal pyrolysis yield can be attained. Yaashikaa et al. combustion products from the pyrolysis process are removed and the
(Yaashikaa et al., 2019) studied that longer residence times at low py- formation of crystalline carbon are promoted in the biochar (Wang and
rolytic temperatures result in higher biochar output. The repolymeriza- Wang, 2019). The total pore volume of steam-activated biochar is higher
tion and condensation reactions that occur between the solids and va- compared to CO2 -activated biochar. This may be attributed to the fact
pors produced are mostly responsible for this. that the size of water molecules is smaller than that of CO2 , thus facil-
itating the diffusion of steam into the pores and the formation of more
O-containing functional groups on the surface of the biochar. There-
4.4. CO2 adsorption on functionalized and activated biochars fore, steam-activated biochar is usually more useful than CO2 -activated
biochar during CO2 capture (H. Zhao et al., 2018).
Raw biochar has a low capability for CO2 adsorption, while the abil-
ity of modified biochar to adsorb CO2 has been demonstrated. in many C + H2 O → H2 + CO (1)
studies (P.D. Dissanayake et al., 2020).Chemical activation methods ex-
pose the biochar to acidic or alkaline solutions that oxidize the surface 2C + H2 → 2CH (2)
and create oxygen-containing functional groups. And the biochar’s sur-
face areas are increased through physical activation that involve forcing H2 O + CO → H2 +CO2 (3)
high-temperature steam through the material’ pores. Steam or acidic
or alkaline solutions are used to activate biochar, resulting in a net- 4.4.2. Chemical modification
work of linked micropores that increase the oxygen-containing func- 4.4.2.1. Alkali-modified biochar. Alkali activation is normally per-
tional groups or enlarge the surface area of biochar (Fig. 7). Controlling formed by soaking and stirring biomass or biochar in an alkaline solution
pyrolysis parameters, feedstock precursors, and activating procedures for several hours. Alkaline metals and alkaline-earthy metals may help
alters the physio-chemical characteristics of biochar (Tan et al., 2017; to produce base sites with a high affinity for acid CO2 , then enhance
Qian et al., 2015). Traditional biochar preparation processes make it dif- the acid-base chemistry between CO2 and biochar. As a result, alkaline
ficult to modulate material shape, porosity, and surface chemical char- metals and alkaline earth metals may improve CO2 adsorption ability
acteristics, which restrict the use of pristine biochar. As a result, the (Xu et al., 2016).
modification of biochar is essential to enhance its specific surface area The activation of biochar using potassium hydroxide or sodium hy-
and porosity, generate new functional groups (Bamdad et al., 2018), and droxide increases the oxygen content and surface basicity of the biochar
improve the structural stability. (Fan et al., 2010; Li et al., 2014). Compared to KOH, NaOH, as a more
economical option, is less corrosive to the biochar, resulting in smaller
4.4.1. Physical modification micro-pores and specific surface area of the resulting biochar. Kaya
Physical modification of biochar does not require the use of expen- (Kaya and Uzun, 2021) et al. impregnated the pyrolyzed pine cone car-
sive chemicals and is much simpler and more economical. As a result, it bon using a concentrated KOH solution and obtained biochar with a
has more applications in practical research. Specifically, biochar is gen- BET surface area of 1714.5 m2 /g, which showed a significant increase
erally subjected to a desired volume of steam, ozone, carbon dioxides, or in surface area compared to the unactivated biochar (259.63 m2 /g) and
air employing an oxidizing agent for physical modification (Sajjadi et al., a maximum adsorption capacity of 3.64 mmol/g for CO2 .This may be
2019). attributed to the fact that when activated with KOH, the carbon and
One of the most extensively used physical treatments for the for- the KOH solution and the formation of new functional groups, such as
mation of tailored biochar is the activation of biochar using CO2 . CO2 K2 CO3 (Basta et al., 2009), which promoted the generation of pores.
activation improves the micropores of biochar, which promotes CO2 Moreover, the author mentioned that the pine cone char activated with
adsorption, according to several studies (Guo et al., 2009). The CO2 KOH had a larger surface area and a higher adsorption capacity than
adsorption capacity of CO2 -modified biochar was significantly higher the char activated with HCl under the same conditions. The higher BET
than that of pristine biochar (Mahmoud et al., 2015). During the CO2 surface area and ultra-micropore and super-micropore volume of KOH-
activation procession, CO2 undergoes dissociative chemisorption on the activated biochars were larger than those of CO2 and steam-activated
biochar surface, forming surface oxides and CO. The surface oxides are biochars, resulting in a considerable improvement in CO2 adsorption
subsequently desorbed from the surface and further develop the pore. capacity. (Shahkarami et al., 2015). Similar phenomenon has been ob-
González et al. (González and Manyà, 2020). used olive mill wastes as served by Igalavithana et al. (Igalavithana et al., 2020) that the KOH
biochar precursor, which were carbonized at 350 °C, followed by ac- activation accelerated the development of micropores and thus the sig-
tivation under CO2 at 900 °C for 1 hour. The modified biochar exhib- nificant increase of CO2 adsorption capacity. To enhance basicity, the
ited a higher CO2 uptake capacity of 129.61 mg/g than unactivated surface area of biochar could also be increased by pre- and, or post-
biochar. The improved CO2 uptake capacity was due to the improved treatment, where KOH is the most commonly used activation agent
BET surface area after CO2 activation (1135m2 /g), compared with that (Serafin et al., 2021).

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Fig. 7. Comparison of unactivated biochar and biochar acti-

vated physically with steam or chemically activated with acid,
oxidant or alkaline solution. (Sizmur et al., 2017).

4.4.2.2. Amine-modified biochar. The N-functional groups of biochar ble, with the CO2 adsorption capacity decreasing by around 20% after
are closely related to its performance in CO2 capture, as discussed in ten cycles. Riya (Chatterjee et al., 2018) described a novel biochar acti-
Section 4.2.2. Biochar is usually capable of capturing CO2 by physical vation way that combines physicochemical activation for CO2 capture.
uptake, and incorporation of amine species reduces the surface area and The amine-modified biochar that had been ultrasound-treated was em-
pore volume of biochar and leads to a reduction in CO2 capture capacity ployed for CO2 adsorption. Raw biochar has a relatively poor adsorp-
(Chen et al., 2014). In some cases, the CO2 capture capacity from the tion capacity of 0.3 mmol/g but following physical modification with
introduced amine species does not compensate for the CO2 capture ca- ultrasound and chemical activation with amine, its capacity was im-
pacity through the loss of physical uptake due to the reduction in active proved to 2.79 mmol/g at 70 °C. The modified biochar retained 56%
surface area. On the other hand, the introduction of amines in biochar of the initial adsorption capacity after 15 cycles, and amine function-
changes the adsorption mechanism from physisorption to chemisorption alization of biochar was accomplished at 35 °C with almost no tem-
or combined physisorption (depending on the amine loading), which perature rise. Biochar was first treated with ultrasonic irradiation for
can enhance the selectivity for CO2 at relatively high temperatures. 30 s, then chemical amination at ambient temperature. From Fig. 8, it
Solid sorbents ornamented with basic amine groups have been shown was discovered that ultrasound exfoliated charcoal graphene clusters,
to have a greater CO2 adsorption capability in previous investigations cleansed, and opened clogged micropores, and enhanced surface area.
(Shafawi et al., 2021). Surface treatment with amine reagents can attach CO2 adsorption was enhanced by the formation of covalent bonds be-
particular functional groups to the solid surface, such as alkyl-amines, tween the nucleophilic active sites on the modified biochar surface and
to improve the CO2 adsorption capability. Urea is frequently used to in- the electrophilic CO2 molecules. However, excessive concentrations of
troduce nitrogen into biochar materials, because urea is a nontoxic and N functional groups, on the other hand, may block the micropore en-
inexpensive amine group (Qiao and Wu, 2022; Rouzitalab et al., 2018; trance and lower the surface area (Zhang et al., 2014). Therefore, it can
Qiao et al., 2020).Qiao et al. (Qiao et al., 2020). prepare biochar by a be concluded that the combination of physical and chemical activation
one-step method of modifying AD digestate by urea and obtained a high can lead to biochar adsorbents with more micropores and better adsorp-
CO2 adsorption capacity (1.22 mmol/g). tion capacity.
For instance, Bamdad et al. (Bamdad et al., 2018) employed meth-
ods for amine functionalization of biochar, i.e. nitration and conden-
sation of aminopropyl triethoxysilane. They found the nitrogen-doped 4.4.3. Other modification methods
biochar exhibited a CO2 adsorption capacity of 165.04 mg/g, which There are also recent new biochar modification methods includ-
was more than double that of the original biochar (79.22 mg/g). In ad- ing ultrasonic treatment (Amin and Chetpattananondh, 2019), electro-
dition, the cycle performance of the modified biochar was rather sta- chemical treatment (Yang et al., 2019; Zoroufchi Benis et al., 2021),

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

Fig. 8. SEM image of a) biochar after ultrasonic activation, b) biochar after ultrasonic physical activation and amine chemical treatment (Chatterjee et al., 2018).

magnetic biochar (Zhou et al., 2019), metal-impregnation treatment biomass by adding another non-biomass (e.g., waste plastics, coal,
(Creamer et al., 2016) and plasma-treated biochar (Wang et al., 2018). and chemicals) could produce biochar with high adsorption capac-
The researchers improved the CO2 adsorption performance of ity.
biochar by using metal impregnation with sodium, magnesium, cal- 3. Different modification methods have various effects on the physico-
cium, nickel, iron and aluminum salts (Zubbri et al., 2020). Lahijani chemical properties of biochar. In addition to the traditional physical
(Lahijani et al., 2018) produced biochar from walnut shells and added and chemical modifications, there are also some emerging modifica-
several metals(magnesium, aluminum, iron, nickel, calcium, sodium) tion methods, including ultrasonic modification, microwave modifi-
into the biochar skeleton by impregnation treatment and heat treat- cation, plasma modification and electrochemical modification tech-
ment. Among these biochars, biochar loaded with Mg has the maximum niques that can adjust the surface functional groups and surface area
CO2 capture capability (80.0 mg/g), and metalized biochar additionally of biochar. Therefore, more modification methods can be developed,
showed a high selectivity for CO2 over other emissions including N2 , and even combined modification of two or more methods can be at-
O2 , CH4 and other gasses. tempted.
Traditional doping procedures (in situ doping and post-treatment 4. Many studies have been conducted on various biochar production
with heteroatom-containing chemicals) typically alter the textural prop- technologies and processes, but they are all general studies with-
erties of porous biochar, but also introduces introduce additional fil- out detailed evaluation of the definite correlation between biochar
tration cycles or hazardous dopants. Plasma treatment of biochar is a characteristics and raw materials, manufacturing processes, or mod-
new method that enables for the quick and cost-effective activation of ifications that can be established to produce biochar with higher
biochar at low temperatures. Wu et al. (2020) prepared biochar which CO2 capture capacities. This work can benefit with raw material se-
was modified by non-thermal plasma treatment in air. Plasma-treated lection, production process adjustments and optimization, together
carbon outperformed for CO2 capture in both pure CO2 atmospheres with more efficient biochar applications.
and complex flue gasses. This could be ascribed to the formation of ni- 5. Currently, most of the studies on the adsorption of CO2 by modified
trogen and oxygen functional groups on the surface of the biochar after biochar have been conducted in the lab scale. The practical environ-
plasma treatment. ment is more complex and harsher than the laboratory environment,
which may contain additional gasses such as nitrogen oxides and sul-
5. Future prospects fur oxides, leading to uncertainties in the environmental impact of
modified biochar. For the practical application of activated biochar,
The application of biochar is of significant potential in CO2 capture the dynamic adsorption, capturing CO2 from complex gas mixtures
due to its abundant sources, developed pore structures and relatively at different temperatures and pressures, and its deactivation resis-
high adsorption capacity. However, there are still some shortcomings tance in harsh practical environments need to be studied in details.
and limitations on its application in CO2 capture, and some more efforts 6. Biochar is stable and persists in the environment for a long time.
has to be carried out as follows: Therefore, the development of environmentally friendly biochar
composites is an important research direction. The potential ecotox-
1. CO2 adsorption capacity of biochar is lower than commercial acti-
icity of biochar materials should be assessed before their introduc-
vated carbon and the adsorption performance needs to be further
tion, the conversion process of biochar should be further studied and
optimized and improved. Possible approaches include optimizing
followed. The life cycle of biochar should be accurately evaluated,
the synthesis conditions and raw material selection to reduce the
and various pollutants need to be assessed both after production and
presence of contaminants in the raw material and reaction process,
after application to reduce secondary pollution.
increasing the specific surface area, pore volume and surface func-
tional groups of biochar, introducing surface functional groups, load-
ing alkali and alkaline earth metals to improve the adsorption per- 6. Conclusions
formance of biochar.
2. For biochar with co-pyrolysis of multiple feedstocks, further analysis Due to the inherent properties of biochar, it has the potential to be
is also needed to determine whether the components of the different a cost-effective and sustainable material for CO2 adsorption. This paper
types interact with each other and whether the prepared biochar in- reviews various production processes of biochar, and the mechanism of
teracts with each other during the adsorption process. Furthermore, CO2 adsorption by biochar. In addition, effect of feedstocks and pyroly-
in the future, it could be investigated whether co-decomposition of sis conditions on the physicochemical properties and CO2 uptake capac-

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S. Guo, Y. Li, Y. Wang et al. Carbon Capture Science & Technology 4 (2022) 100059

ities was described in detail. Apart from that, the modification plays a Goldfarb, J.L., Dou, G., Salari, M., Grinstaff, M.W., 2017. Biomass-based fuels and acti-
crucial role in the CO2 adsorption capacity of biochar. The surface area, vated carbon electrode materials: an integrated approach to green energy systems.
ACS Sustainable Chem. Eng. 5, 3046–3054.
micropore area, micropore volume, presence of basic functional groups Lee, J., Kim, K.H., Kwon, E.E., 2017. Biochar as a Catalyst. Renewable Sustainable Energy
and hetero atoms all contribute significantly to the CO2 adsorption ca- Rev. 77, 70–79.
pacity of biochar. Various physical and chemical modification meth- Mian, M.M., Liu, G., 2020. Activation of peroxymonosulfate by chemically modified sludge
biochar for the removal of organic pollutants: understanding the role of active sites
ods have been discussed and compared. However, there have been few and mechanism. Chem. Eng. J. 392, 123681.
large-scale applications of biochar for CO2 capture, and more research Shafeeyan, M.S., 2010. A review on surface modification of activated carbon for carbon
is needed to investigate the definite relationship between raw materi- dioxide adsorption. J. Anal. Appl. Pyrolysis 9. doi:10.1016/j.jaap.2010.07.006.
Sizmur, T., Fresno, T., Akgül, G., Frost, H., Moreno-Jiménez, E., 2017. Biochar modifica-
als and production conditions with biochar properties by machine/deep
tion to enhance sorption of inorganics from water. Bioresour. Technol. 246, 34–47.
learning, as well as to propose new modification methods for improve- Dissanayake, P.D., et al., 2020a. Biochar-based adsorbents for carbon dioxide capture: a
ment of CO2 adsorption capacity. critical review. Renewable Sustainable Energy Rev. 119, 109582.
Jung, S., Park, Y.-.K., Kwon, E.E., 2019. Strategic use of biochar for CO2 capture and
sequestration. J. CO2 Utilization 32, 128–139.
Declaration of Competing Interest de Kleijne, K., et al., 2022. Limits to Paris compatibility of CO2 capture and utilization.
One Earth 5, 168–185.
Gao, W., et al., 2020. Industrial carbon dioxide capture and utilization: state of the art
All authors declare that they have no financial orpersonal conflicts and future challenges. Chem. Soc. Rev. 49, 8584–8686.
of interest. Salehizadeh, H., Yan, N., Farnood, R., 2020. Recent advances in microbial CO2 fixation
and conversion to value-added products. Chem. Eng. J. 390, 124584.
Mustafa, A., Lougou, B.G., Shuai, Y., Wang, Z., Tan, H., 2020. Current technology devel-
Acknowledgement opment for CO2 utilization into solar fuels and chemicals: a review. J. Energy Chem.
49, 96–123.
Osman, A.I., Hefny, M., Abdel Maksoud, M.I.A., Elgarahy, A.M., Rooney, D.W, 2021. Re-
The authors gratefully thank National Natural Science Foundation cent advances in carbon capture storage and utilisation technologies: a review. Envi-
of China (Project No. 21976011 and 22006075) for providing financial ron. Chem. Lett. 19, 797–849.
support. Kheirinik, M., Ahmed, S., Rahmanian, N., 2021. Comparative techno-economic analysis of
carbon capture processes: pre-combustion, post-combustion, and oxy-fuel combustion
operations. Sustainability 13, 13567.
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