Research On Carbon Dioxide Capture Materials Used For Carbon Dioxide Capture, Utilization, and Storage Technology: A Review

Environmental Science and Pollution Research (2024) 31:33259–33302
https://doi.org/10.1007/s11356-024-33370-2
REVIEW ARTICLE
Research on carbon dioxide capture materials used for carbon dioxide

capture, utilization, and storage technology: a review
Hongtao Dang1 · Bin Guan1 · Junyan Chen1 · Zeren Ma1 · Yujun Chen1 · Jinhe Zhang1 · Zelong Guo1 · Lei Chen1 ·
Jingqiu Hu1 · Chao Yi1 · Shunyu Yao1 · Zhen Huang1
Received: 15 December 2023 / Accepted: 13 April 2024 / Published online: 3 May 2024
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2024
Abstract
In recent years, climate change has increasingly become one of the major challenges facing mankind today, seriously threat-
ening the survival and sustainable development of mankind. Dramatically increasing carbon dioxide concentrations are
thought to cause a severe greenhouse effect, leading to severe and sustained global warming, associated climate instability
and unwelcome natural disasters, melting glaciers and extreme weather patterns. The treatment of flue gas from thermal
power plants uses carbon capture, utilization, and storage (CCUS) technology, one of the most promising current methods
to accomplish significant C O2 emission reduction. In order to implement the technological and financial system of CO2
capture, which is the key technology of CCUS technology and accounts for 70–80% of the overall cost of CCUS technol-
ogy, it is crucial to create more effective adsorbents. Nowadays, with the development and application of various carbon
dioxide capture materials, it is necessary to review and summarize carbon dioxide capture materials in time. In this paper,
the main technologies of CO2 capture are reviewed, with emphasis on the latest research status of CO2 capture materials,
such as amines, zeolites, alkali metals, as well as emerging MOFs and carbon nanomaterials. More and more research on
CO2 capture materials has used a variety of improved methods, which have achieved high C O2 capture performance. For
example, doping of layered double hydroxides (LDH) with metal atoms significantly increases the active site on the surface
of the material, which has a significant impact on improving the C O2 capture capacity and performance stability of LDH.
Although many carbon capture materials have been developed, high cost and low technology scale remain major obstacles
to CO2 capture. Future research should focus on designing low-cost, high-availability carbon capture materials.
Keywords CCUS · CO2 capture · Amines · Zeolite · Metal–organic framework · Alkali metal · Layered double hydroxides
Research background Excessive greenhouse gas emissions will trigger global

greenhouse effect, which will lead to global warming, ocean
CO2 emissions and their hazards acidification, extreme weather and other environmental
problems, and eventually cause great damage to the earth
Since the first Industrial Revolution, as industrialization on which human beings depend for survival. According to
has advanced in a number of nations, human beings have meteorological changes in the northern mid-latitudes, the
an increasing demand for energy, especially fossil energy. duration of extreme weather such as heat waves, droughts,
The exploitation and combustion of fossil energy will inevi- and rain periods is likely to increase if the global temper-
tably lead to a large amount of greenhouse gas emissions. ature increases by 2 ℃ above pre-industrial levels, while
these conditions can be avoided by warming within 1.5 ℃.
Therefore, the goal of the Paris Agreement formulated by
Responsible Editor: Tito Roberto Cadaval Jr the United Nations is to limit the degree of global warming
to 1.5 ℃ higher than the pre-industrial level, so as to reduce
* Bin Guan
[email protected] the natural disasters and species extinction brought by the
greenhouse effect (Seneviratne et al. 2018).
1
Key Laboratory for Power Machinery and Engineering Massive emissions of greenhouse gases, mainly CO2,
of Ministry of Education, Shanghai Jiao Tong University, lead to global climate change. This harmful impact is one
Shanghai 200240, China
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33260 Environmental Science and Pollution Research (2024) 31:33259–33302
of the most challenging and urgent impacts facing the world majority of carbon dioxide emissions. Since fossil energy
today. The growth of global population and the resulting O2 in the process of use and combustion, it
releases a lot of C
energy demand will lead to continued increase of CO2 emis- must be captured and reduced to achieve the goal of “double
sions and make global warming more serious (Guesmi et al. carbon.” CO2 capture methods are numerous, according to
2022; Baaloudj et al. 2023). Global warming will not only the way can be divided into porous material physical adsorp-
pose a direct threat to the survival of the present generation, tion, polymer gas separation membrane, alcohol amine, car-
but will also adversely affect future generations through the bonate, alkaline solution chemical absorption methods. The
destruction of ecosystems, droughts and floods, and other concentrated CO2 is transferred after being captured until it
extreme climate phenomena (Badawi et al. 2023; Mater et al. can be utilized again or permanently stored. The C O2 that is
2023). Recently, sensors at NOAA’s Mauna Loa weather captured can be raw materials for chemical production, or
station detected a startling reading that atmospheric carbon to improve the concentration of C O2 in the greenhouse to
dioxide concentrations crossed the 400 ppm red line in 2016 achieve the purpose of improving photosynthesis. Addition-
and reached 414.7 ppm in May 2019. The concentration of ally, carbon dioxide can be permanently stored in exhausted
carbon dioxide in the atmosphere is expected to reach 500 oil and gas fields to prevent it from contributing to the green-
parts per million by 2050 (Yang 2022). The burning of fos- house effect. It can also be injected into oil wells to aid in
sil fuels (coal, oil, and natural gas) by factories and thermal the extraction of oil and gas.
power plants accounts for about 45% of global CO2 emis- As an emerging and immature technology, the commer-
sions. As one of the main greenhouse gases in the earth’s cialization of CCUS depends on supportive policy frame-
atmosphere, carbon dioxide will have a great impact on cli- works and investment incentives. By slowing the adoption
mate change. Various studies have suggested that the con- of technology, the viability of CCUS is compromised by its
centration of carbon dioxide in the atmosphere should be cost, while scaling and deploying full-chain infrastructure
limited to 350–450 parts per million (Elawwad et al. 2017; requires significant capital expenditures (Martin-Roberts
Badawi et al. 2022). et al. 2021). High operating costs due to the large energy
requirements of capture, transport, and storage systems
CCUS technology further inhibit the deployment of the technology, while
the viability of various CCUS processes remains similarly
Carbon dioxide capture, utilization, and storage (CCUS) constrained due to energy-related costs and the high cost
technology is an important emerging method for C O2 emis- of obtaining suitable chemical feedstocks, making certain
sion reduction in recent decades. With the emergence of synthetic pathways (e.g., green fuels, mineral carbonization)
increasingly serious climate problems, this measure has economically unviable (Lane et al. 2021; Azadi et al. 2019;
become a research hotspot. As a relatively effective miti- Akerboom et al. 2021). On the other hand, the application
gation measure, it represents an indispensable role in C O2 of CCUS technology lacks an effective business model, and
emission reduction. CCUS technology mainly involves five various factors need to be overcome to improve the eco-
parts, namely CO2 emission, capture, transport, utilization, nomic viability of CCUS, including how to share and trans-
and storage. The post-combustion capture pathway is consid- fer financial risks, as well as solve the financing problems of
ered to be the most feasible solution for CO2 capture (Kang related projects (Martin-Roberts et al. 2021).
et al. 2020), and its process flow and key components are Therefore, relevant studies have emphasized the need for
shown in Fig. 1a, which mainly include a CO2 capture com- financial support in the form of tax credits, subsidies, direct
ponent and a CO2 compression component. The enhanced government financing, or grants (Akerboom et al. 2021;
oil recovery using CO2 (CO2-EOR) and methanol synthesis Martin-Roberts et al. 2021). Financial support is seen as
from captured CO2 (CO2-MET) are common processes for key to the overall viability of CCUS, as it helps overcome
CO2 storage and CO2 utilization, respectively. As shown first mover disadvantages and encourages private invest-
in Fig. 1b, CO2-EOR includes a CO2 injection assembly ment by lowering upfront capital requirements while miti-
(consisting of C O2 pipeline transportation and injection gating financial security in the face of uncertain costs (Beck
wells) and a production separation assembly (consisting of 2019; Lane et al. 2021). In addition, market drivers affect
extraction wells, product handling and separation units). As the economic viability of CCUS, and effective C O2 pricing
shown in Fig. 1c, the C O2-MET includes a methanol syn- is needed to ensure that penalties for CO2 emissions drive
thesis assembly (consisting of a feedstock buffer tank and emitters to adopt mitigation technologies such as CCUS
a methanol synthesis tower) and a purification distillation (Cao et al. 2020).
assembly (consisting of a high temperature heat exchanger, The viability of CCUS also depends on public accept-
a crude methanol–water cooler, and a methanol separator). ance of these technologies, which is influenced by trust
At present, industrial sectors such as petrochemicals, in key stakeholders, negative associations between car-
steel, and coal-fired power generation account for the bon capture and the fossil fuel industry, perceived safety
Environmental Science and Pollution Research (2024) 31:33259–33302 33261
Fig. 1 Process flow and key

components of CCU technol-
ogy. Reprinted with permission
from (Liu et al. 2022). Copy-
right 2022 Elsevier
risks, and the extent and form of public consultation the continued approval of a particular project by the local
(Sharma 2018; Dean et al. 2020). Public acceptance of community or group of actors and are considered impor-
CCUS includes two dimensions: sociopolitical acceptance tant in helping to build investor confidence in a particular
and community acceptance (Jones et al. 2017). Increased initiative (Cao et al. 2020).
public acceptance not only strengthens social support for Providing people with more information can help indi-
energy policies, but also weakens barriers to negotiation viduals make informed decisions about technology. There-
between businesses and communities (Qi et al. 2020). fore, a multi-channel communication mechanism should be
Historically, lack of public acceptance has proven to be established, including the organization of technical semi-
a key barrier to various CCUS initiatives and policies, nars, the establishment of community reference groups,
particularly in onshore CCUS projects, often due to pub- and the public disclosure of CCUS program information.
lic concerns about the long-term safety of CO 2 storage By informing citizens about the program in a timely man-
(Akerboom et al. 2021). The public reaction has been ner and adequately addressing laymen's concerns, common
interpreted as a “not in my backyard” tendency or a lack misconceptions about CCUS can be eliminated.
of understanding of the technology (Martin-Roberts et al. Providing people with more information can help indi-
2021). While public acceptance may be key to project ini- viduals make informed decisions about technology. There-
tiation, the social license to operate (SLO) is seen as criti- fore, a multi-channel communication mechanism should
cal to its long-term success. In particular, SLO describe be established, including the organization of technical
seminars, the establishment of community reference groups, The economics of carbon capture can be improved
and the public disclosure of CCUS program information. through technological advances, infrastructure development,
By informing citizens about the program in a timely man- revenue from carbon utilization, credit sales, or carbon tax
ner and adequately addressing laymen’s concerns, common incentives (Kotagodahetti et al. 2022). Innovations in car-
misconceptions about CCUS can be eliminated (Linzenich bon capture technology have evolved over time, leading to
et al. 2019). Trust is an important situational contextual process improvements and cost reductions. Significant cost
factor. Unlike the first CCUS projects, there are successful reductions can only be realized through continued research
demonstration projects around the world, which increases and development and long-term investment. However, a mar-
the attractiveness of the technology (Tcvetkov et al. 2019). ket-based CCUS strategy can only be achieved through gov-
To enhance public trust, it is recommended that project ernment action. This highlights the importance of rigorous
organizers work with experienced third parties to learn from policy measures to promote carbon capture and incentive
the experiences of international demonstration projects and programs. These measures can accelerate the deployment of
to demonstrate that they can deliver on their commitments carbon capture technologies and realize future reductions in
under the project. carbon capture costs.
In this technology, CO2 capture, as the second step, is the
most important step for CO2 emission reduction, and also the Absorption separation method
most expensive process in CCUS technology, accounting for
about 85% of the entire CCUS process (Sarker et al. 2017). Among various CO2 separation methods, absorption separa-
The amine chemical absorption method is the most mature tion is the most widely used method at present. The tradi-
technology of C O2 capture in flue gas after combustion. tional absorption and separation method realizes the separa-
Although amine absorption is the most mature and widely tion of CO2 by washing the mixed gas with the absorptive
used technology for C O2 absorption in industry, it has some solution. Its technology is relatively mature and widely used.
problems such as huge energy consumption and corrosion According to the different kinds of absorptive solvent used,
of equipment. Therefore, how to design and produce absor- the absorption and separation method is mainly divided
bent with high absorption rate, high stability, and adjustable into physical absorption method and chemical absorption
performance is an urgent problem to be solved in academic method, which generally includes the absorption of carbon
and industrial circles. dioxide and the regeneration of solvent.
Physical absorption method

Separation of CO2
The physical absorption method utilizes the principle that
At present, the main methods for separating carbon dioxide the carbon dioxide in the raw gas has a greater solubility in
from flue gas are absorption separation, adsorption sepa- the absorptive solution. It can absorb and desorption car-
ration, membrane separation, and low temperature distilla- bon dioxide by alternately changing the temperature and
tion. Their key technical and economic parameters (e.g., C
O2 pressure, so as to achieve the purpose of separating and
removal efficiency, C
O2 capture energy consumption, and capturing CO2. Generally, low temperature and high pres-
CO2 capture cost) are shown in Table 1, which, in addition sure are used for absorption, while high temperature and
to the operating parameters and the gas composition of the decompression are used for desorption. The decompression
gas streams to be processed, are useful information when desorption requires less regenerative energy. The key of this
selecting a C
O2 separation technology for a particular CCUS method is the selection of absorbing solvent. The solvent for
project. These C O2 separation technologies are described absorbing CO2 requires that CO2 has high solubility in solu-
in the following sections (sections “Absorption separation tion, no corrosion, good selectivity, and stable performance.
method” to “Low temperature distillation”). Commonly used absorption solvents are water, methanol,
Table 1 CO2 removal efficiency, energy consumption, and cost of C

O2 capture of different separation technologies
CO2 separation technology CO2 removal efficiency Energy consumption for C
O2 CO2 capture cost Ref
(% vol.) capture (GJ/t C
O2) (USD/t CO2)
Absorption (MEA) 85 to 90 3.80 62.80 Yun et al. (2020)

Adsorption (13 X zeolite) 85 to 90 1.17 89.66 Cheng et al. (2021)
Membrane (polymeric material) 70 to 90 1.28 80.46 Zanco et al. (2021)
Cryogenic (packed bed) 90 to 99.99 1.80 52 Depeng et al. (2019)
trin-butyl phosphate, n-methylpyrrolidone, polyethylene stability of the solvent itself, it was gradually replaced by
glycol dimethyl ether, propylene carbonate, polyethylene MEA method (ethanolamine) and DEA method (diethan-
glycol methyl isopropyl ether and formylmorph derivatives, olamine). Ammonia plants mainly use MEA method, which
etc. Typical physical absorption methods are pressure wash- has the advantages of strong absorption of C O2 selectivity
ing method, propylene carbonate method, low temperature and large absorption amount; absorption rate is fast, desorp-
methanol method, N-methylpyrrolidone method, Selexol tion thoroughly. The absorption process uses less power. The
method, and so on. disadvantage is that the solution regeneration consumes a
The physical absorption method is usually carried out at lot of heat, and the corrosion of the equipment is serious.
low temperature and high pressure. Its advantages are simple It is not suitable for the absorption of C
O2 in the mixed gas
process, large amount of CO2 absorption, less amount of with high oxygen content and the solution is easy to be oxi-
absorbent, no need for heating. The method of step-down dized and degraded. Figure 2 shows the mechanism of CO2
or normal temperature stripping is adopted, so the energy absorption by MEA/sulfolane phase change solvent. First, a
consumption is low, and the investment and operating costs single liquid phase of MEA/sulfolane aqueous solution was
are also low. However, since the dissolution of CO2 in sol- fed into the absorber. Due to the strong affinity of sulfolane
vents obeds Henry’s law, this method is most suitable for for CO2, sulfolane acts as a physical solvent and promotes
situations where the partial pressure of CO2 is high and the the physical diffusion of CO2 in water. When in contact with
degree of CO2 removal is not required, such as the purifica- CO2, the sulfolane captures CO2 molecules at the gas/liquid
tion of syngas. interface and passes them to the MEA for further absorp-
tion reaction. MEA reacted with C O2 to form carbamate
and protonated MEA. As the C O2 absorption reaction pro-
Chemical absorption method ceeds, the concentration of the carbamate and protonated
MEA gradually increases. When the concentration of the
Chemical absorption method is to use the chemical reaction carbamate and protonated MEA reaches a certain concentra-
between CO2 and solvent to achieve the absorption and des- tion, the immiscibility between hydrophilic carbamate and
orption of carbon dioxide, because C O2 is weakly acidic, so hydrophobic sulfolane triggered phase separation, and the
it can be absorbed by alkaline solution and removed. Chemi- sulfolane gradually settled at the lower layer, leaving a high
cal absorption method is usually carried out in the absorp- CO2 concentration in the upper phase.
tion tower, the solution and carbon dioxide reaction, carbon As a traditional C O2 removal method, chemical absorp-
dioxide is absorbed by the solution, and then the solution tion method has high purity and large processing capacity
into the desorption tower through heating decomposition, after removal, and its research and application are relatively
carbon dioxide is released, so as to fulfill the goal of CO2 mature and in-depth. The chemical absorption method is
capture. Traditional chemical absorption methods include mainly suitable for the treatment of various kinds of mixed
hot potassium alkali method and alcohol-amine method. gases with low partial pressure of CO2 and large flow rate.
The hot potassium-alkali process uses the hot solution However, the chemical absorption method also has some
of strong alkaline carbonate as the absorption solvent to drawbacks, for the process operation is more complicated in
achieve the absorption of CO2. The principle of absorption the aspect of recycling. Moreover, the chemical absorption
of CO2 by hot potassium alkali method is to use K2CO3 solu- method is not suitable for the absorption of mixed gases
tion to absorb CO2 and generate KHCO3 (called rich liquid) containing CO2, which requires complex treatment system,
to separate C O2. After heating the rich solution, K HCO3 and most of the absorption solvents are corrosive liquids.
decomposes and releases CO2 to form K2CO3, and the solu- The corrosion of the equipment is more serious. As a wet
tion is recycled. The reaction formula is as follows: process, the process of chemical absorption method is rela-
K2 CO3 + CO2 + H2 O ⇌ 2KHCO3 tively complicated. The fluid needs periodic temperature rise
and fall, a large amount of external heating energy is needed
The hot potassium-alkali process and various improved for solution regeneration, and the investment and operation
processes developed on the basis of it are one of the impor- cost are also high.
O2 removal, especially in the synthesis of
tant methods for C
ammonia industry. Adsorption separation method
The chemical absorption methods using ethanol-amine
as absorbers mainly include MEA method (monoetha- Water solvent has a high selectivity for C O2 absorption.
nolamine), DEA method (diethanolamine), and MDEA Its main disadvantage is that the solvent consumes a high
method (n-methyldiethanolamine). TEA method (triethan- amount of energy in the regeneration process, which con-
olamine) was used earlier in industry, but due to the low sumes about 30% of the total output of the power plant.
CO2 absorption efficiency of triethanolamine and the poor Therefore, it is particularly urgent to develop an economical,
Fig. 2 Mechanism of C O2
capture when using the aqueous
MEA/sulfolane phase change
solvent. Reprinted with permis-
sion from (Wang et al. 2018a).
Copyright 2018 American
Chemical Society
efficient and environmentally friendly CO2 capture technol- van der Waals forces (Sarker et al. 2017). Compared with N 2
ogy suitable for existing power plants (Bahamon and Vega and CH4, CO2 has a higher polarization of 29.1 × 10−25 cm3,
2016). The adsorption process requires that the adsorbate which is conducive to the electrostatic adsorption of adsor-
can be effectively removed from the adsorbent during the bent on its surface. In addition, thermodynamic equilibrium
regeneration process and the adsorption cycle time. The and the diffusion rate of the compound determine the selec-
adsorption performance is affected by the operating condi- tive adsorption of C O2 on the adsorbent surface (Kacem
tions, including the reactor’s temperature and pressure, the et al. 2015).
type of gas and so on (Kacem et al. 2015). The recycling of adsorbents after adsorption of C O2
During the adsorption process, C O 2 is selectively from flue gas has been extensively studied. The cyclic
adsorbed on the surface of the adsorbent through different adsorption of adsorbents is completed through the fol-
mechanisms (chemisorption or physical adsorption) (Bhown lowing three regeneration processes: (i) temperature
and Freeman 2011). In the physical adsorption process, the swing adsorption (TSA), (ii) pressure swing adsorption
adsorbent needs to have a high specific surface area and a (PSA), and (iii) vacuum pressure swing adsorption (VSA)
porous structure to adsorb the adsorbate on its surface with (Krishnamurthy et al. 2014). Carbon dioxide is desorbed
the help of electrostatic attraction and van der Waals forces. by reducing the pressure in the adsorption tower during
During the chemisorption process, the adsorbate is adsorbed PSA and VSA processes. The difference between PSA and
at the binding site on the adsorbent surface through covalent VSA is that in the PSA process, the adsorption tower is
bonding (Berger and Bhown 2011). first filled with gas until it is saturated, and then the pres-
Different materials have different chemisorption mecha- sure of the adsorption tower is lowered to atmospheric
nisms. For example, metal organic frameworks (MOFs) pressure resulting in gas desorption. In the VSA process,
adsorb CO2 on the surface through unsaturated metal sites the saturated adsorbent uses a vacuum in the adsorption
or special functional groups on the surface. CO2 is adsorbed tower to desorbed the gas (Siqueira et al. 2017; Sumida
on the surface of carbon materials by chemical adsorption et al. 2012). Compared with PSA and VSA, TSA has
through intrinsic functional groups or functional groups received more attention because of its lower energy con-
introduced by chemical modification. Previous studies have sumption in the adsorbent regeneration process, and is
proved that by adding inorganic metal oxides (alkali met- considered to be a potential method for C O 2 capture in
als) or basic organic groups (-NH2), chemical adsorption of industrial applications. In the process of TSA, flue gas
CO2 can be improved. The adsorption materials can chemi- is pumped into the adsorption tower, then heated to its
cally adsorb C O2 in two ways: carbonate and carbamate desorption temperature. The increase of temperature will
(Qaroush et al. 2017). Different theories show that the physi- make the gas molecules free from the surface of the adsor-
cal adsorption of gas molecules on the adsorbents surface bent. The increase of pressure in the adsorption tower and
occurs through the mass transfer process, while the selective the purity of the gas are conducive to the removal of the
adsorption is achieved through electrostatic attraction and desorbed gas from the tower.
The main criteria for selecting adsorbents include spe-

cific surface area, adsorption amount, pore size and pore
volume, density, regeneration capacity, production method,
selectivity, and sustainability of the target gas (adsorbate).
Some typical materials used for C O2 adsorption are zeolite
molecular sieves, activated carbon, MOFs, and silicon mate-
rials. In recent years, the research and development of new
adsorbents has received an increasing amount of interest.
Membrane separation method
Membrane separation is a new physical separation method

that separates CO2 gas from flue gas through semi-permea-
ble membrane. Compared with traditional solvent absorption Fig. 3 Schematic illustration of the gas transport mechanism through
methods, membrane separation technology is cheaper due dense membranes. Reprinted with permission from (Tomé and Mar-
rucho 2016). Copyright 2016 Royal Society of Chemistry
to its low energy consumption (Ansaloni et al. 2017). The
principle of membrane separation method is to realize the
separation of C O2 by using the different velocities of C
O2 through the micropores to the other side of the film under
and other components in the mixed gas through the mem- low pressure, and interact with the absorption solution to
brane material, and the pressure difference is used as the achieve the separation of CO2.
driving force to promote the separation. Membrane separa- In the last 20 years, membrane separation technology
tion technology is divided into two categories: gas separa- has been successfully used in a wide range of selective gas
tion membrane technology and gas absorption membrane separation applications, such as upgraded biogas, hydrogen
technology. production, air separation, and natural gas desulfurization.
The gas membrane separation technology relies on the At present, researchers are doing a lot of work in developing
chemical or physical reaction between the gas mixture to membrane materials that can be used to separate the carbon
be separated and the membrane material to achieve rapid dioxide emitted during the operation of different industries.
dissolution of the gas to be separated (CO2) and passage In addition, membrane separation technology also has cer-
through the membrane. The gas mixture passing through tain advantages from the perspective of economy and envi-
the membrane is divided into a penetrating gas stream and a ronment (Li et al. 2015).
residual gas stream, the central driving force of which is the There are many membrane materials for CO2 separation,
pressure difference between the two sides of the membrane, such as mixed matrix membrane, carbon molecular sieve
as shown in Fig. 3. The separation capacity of gas separa- membrane, polymer membrane and inorganic membrane,
tion membrane technology depends on the selectivity of the etc. (He et al. 2015). Among them, polymer membrane and
membrane material as well as the flux ratio and pressure inorganic membrane are the most widely used. Polymer
ratio of the penetrating gas stream to the total gas stream. membranes for separating C O2 from industrial flue gases
The gas absorption membrane technology absorbs the are generally considered energy efficient, durable, and flex-
high selectivity of the chemical absorption method and the ible. Whether it is glass material or rubber material, the
compact equipment of the separation membrane technology. polymer film can be separated by molecular sieve through
The difference with the separation membrane technology is particle size difference and diffusion principle to achieve
that there is a chemical absorption solution on the other side better CO2 separation effect. However, polymer membranes
of the membrane. In the gas absorption film technology, the are limited in some applications due to their “trade-off”
film material only plays the role of separating the absorbent between permeability and selectivity of gases (Vinoba et al.
solution from the absorbed gas, and the absorbent solution 2017). Compared with polymer films, inorganic films have
is mainly used to separate C O2 gas. The mixed gas enters higher diffusivity and selectivity of gas molecules. In addi-
along one side of the membrane, and the chemical absorption, these inorganic membranes have advantages in terms
tion solution is placed on the other side of the membrane. of thermal and chemical stability, mechanical strength, and
The component CO2 to be separated diffuses to the other side longer lifetime (Lee et al. 2017). However, other parameters
of the membrane through the micropores of the membrane of these membranes, such as the production of defect-free
and is absorbed by the absorption solution, thus achieving membranes, brittleness, and operating costs, limit their
the separation of CO2. Theoretically, when the micropores application (Jamil et al. 2016; He et al. 2015). Therefore,
on the film are large enough, C O2 molecules of the gas to be developing a new membrane technology for gas separation
separated from one side of the film can be allowed to pass that overcomes the boundary between polymer and inorganic
membranes and provides an alternative membrane with bet- economic benefits, process reliability, and operational
ter separation properties is still of interest to researchers. flexibility. On the other hand, due to the large number of
The main aspect of membrane separation for C O2 sepa- CO2 capture devices and the relatively simple operation
ration is the removal of C
O2 from natural gas. This method mechanism of each device, a wide range of criteria can
has the advantages of simple device, high efficiency and be developed to select the right C O 2 capture method.
low investment, and the CO2 itself has strong polarity, high The technical problems associated with CO 2 separation
solubility, high boiling point, and high permeability coef- are well understood and in most cases properly resolved.
ficient and separation coefficient. Therefore, the membrane Determining the process that optimizes energy consump-
separation method is suitable for the separation and enrich- tion plays an important role in determining the most
ment of C O2 under high temperature and high pressure, and appropriate way to separate carbon dioxide from different
it is a promising energy-saving CO2 separation technology. sources. After comparative analysis, the most mature car-
At present, many membrane devices for C O2/CH4 separa- bon capture technology is chemical absorption method,
tion have been developed for industrial applications such which has realized commercial industrial application;
as polyimide, cluster membrane, and cellulose ester. The Both adsorption and membrane separation methods have
disadvantage of membrane separation method is that it is dif- great energy saving potential and application prospects,
ficult to deeply remove and obtain high purity CO2, and the but they are still in the pilot and demonstration stage
loss of hydrocarbons is relatively serious. It usually needs at present, and there is a certain gap between them and
to be combined with alcohol amine solvent process to save industrial applications. Although the low temperature
energy consumption and reduce investment. separation method has the advantages of C O 2 recovery
and purity, its separation process is carried out at low
Low temperature distillation temperature and high pressure, the energy consumption
and cost are relatively high, and it is more suitable for
Separation of CO2 by low temperature distillation requires the separation of high concentration of CO2.
the removal of all components except N2 and C O2 from Through induction, it is found that different carbon cap-
the flue gas prior to cooling. When all other gases and ture technologies have advantages and disadvantages, and
particles have been removed, the remaining gas is sent to no carbon capture method can independently, efficiently,
a cryogenic greenhouse, where the temperature and pres- economically, and energy-saving carbon capture. At pre-
sure are controlled to liquefy the carbon dioxide. Under sent, the focus of application is to select a relatively suit-
appropriate conditions (the triple point temperature of C O2 able trapping method according to the technical character-
is − 56.68 ℃, ~ 7.4 atm), CO2 will condense and accumulate istics after evaluating the key indicators such as technical
at the bottom of the container, while N2 will remain as a reliability and economy. In the future, the development of
gaseous state and escape through the outlet at the top of the high-efficiency and energy-saving carbon capture technol-
chamber. ogy can focus on the problems and challenges existing in
Compared with other separation methods, the advantage the current technologies. It can also combine the advan-
of low temperature distillation is that the recovery rate of tages of various technologies to develop mixed capture
CO2 is very high, and the purity of CO2 after distillation technology to further promote the large-scale development
can exceed 99.95% (Meratla 1997). In addition, because of carbon capture technology.
the product is liquid carbon dioxide, it can be transported
and stored through pipelines or tank trucks. However, the
cryogenic process is very energy intensive, and the energy
required to keep the system cool (usually using liquid nitro- Low temperature CO2 absorbent
gen) makes the separation process too expensive. Another
disadvantage of the cryogenic process is that O2, NOx, SOx, Amine absorbent
and H2O must be removed from the flue gas prior to the
separation process. When the gas enters the chamber and The process of amine solution decarbonization was first
still contains water, the water will freeze and block the pipe, produced in the 1930s and has a history of more than
and it will also corrode the equipment. 80 years. This method has the characteristics of fast C
O2
Selecting the best carbon capture technology is a com- absorption rate, large amount of absorption, low cost, and
plex subject, as a variety of technical and economic fac- the absorbent can be recycled and recovered to high purity
tors need to be considered, including feedstock gas com- CO2. At present, organic amine solution for C O2 capture
position and parameters, required treatment gas purity, is widely used in industry. It occupies more than 60% of
facility costs (investment and maintenance), possible the carbon capture market share (Xie 2022).
Absorption mechanism amine (Saiwan et al. 2011), as shown in reaction 3.5 (where
R1, R2 and R3 are chain anols).
The molecular structure of organic alcoholamine compounds
contains at least one hydroxyl functional group, which can R1 R2 R3 N + H2 O + CO2 ⇌ R1 R2 R3 NH + + HCO3 − (3.5)
reduce saturated vapor pressure and promote water solubil- The initial reaction between sterosteric amines and
ity, and amino functional group, which can promote CO2 CO2 also follows the mechanism of amphoteric absorp-
absorption. In general, organic amines can be classified tion. However, unlike primary and secondary amines, the
into three types based on the number of active hydrogen nitrogen atoms on sterosteric amines have a huge steros-
atoms attached to nitrogen atoms: primary amines (nitro- teric hindrance effect, which makes the generated carbamate
gen atoms are attached to two hydrogen atoms), secondary extremely unstable and prone to hydrolysis into bicarbonate
amines (nitrogen atoms are attached to one hydrogen atom), and free amines, which then react with CO2 again. There-
and tertiary amines (nitrogen atoms do not contain hydrogen fore, theoretically, the C
O2 loading of steric steric amine can
atoms). According to the number of active nitrogen atoms, also reach 1 mol CO2/amine (Choi et al. 2010), and the total
can be classified into monoamine and polyamine. Due to the reaction equation is shown in 3.6.
strong alkalinity of the amino functional group in the amine
molecule, the organic amine can absorb CO2 with fast reac- R1 R2 NH + H2 O + CO2 ⇌ R1 R2 NH 2 + + HCO3 − (3.6)
tion speed and good absorption selectivity.
The absorption mechanism of C O2 by primary and sec- Numerous investigations conducted in recent years have
ondary amines is generally recognized as the “Zwitterion” discovered that the presence of numerous amino groups in
mechanism (Freeman et al. 2010), that is, the reaction polyamines is primarily responsible for their rapid mass
between amine and CO2 is divided into two steps. First, an transfer rate, high chemical reaction rate, and exceptionally
amine reacts with C O2 to form an intermediate zwitterion. strong CO2 absorption ability. For example, diethylenetri-
Then, another amine deprotonates the zwitterion. It makes amine (DETA) contains three amino groups, which can form
a deprotonated product and the Carbamate ion. The specific a variety of carbamate, and its C
O2 loading can exceed 1 mol
reaction formula is as follows (where R1R2 is H atom or CO2/amine. In addition, DETA, as a polyamine, has higher
chain alkanol group): absorption rate (Saiwan et al. 2011), cycling capacity (Bello
and Idem 2005), and lower absorption heat compared with
R1 R2 NH + CO2 ⇌ R1 R2 NH + COO− (3.1) monoamine. DETA is a new efficient C O2 absorbent with
low vapor pressure, low toxicity, low viscosity, and good
R1 R2 NH + R1 R2 NH + COO− ⇌ R1 R2 COO− + R1 R2 NH 2 + water solubility. The properties and method of CO2 absorp-
(3.2) tion by DETA solution and DETA combined with various
amine solutions have been extensively researched (Afkhami-
The total reaction is:
pour and Mofarahi 2017), but there are few studies on the
2R1 R2 NH + CO2 ⇌ R1 R2 NCOO− + R1 R2 NH 2 + (3.3) corrosiveness of DETA mixed with other amine solutions.
According to the total reaction formula, the theoretical

Blended amine solvents
CO2 loading of primary and secondary amine solutions is
0.5 mol CO2/mol amine. However, carbamate generated by
To overcome the drawbacks of employing a single amine to
the reaction of some amines with CO2 may hydrolyze under
absorb CO2, many commercially available combinations of
high CO2 loading to produce free amines and bicarbonate
primary, secondary, and tertiary amines have been created.
(HCO3−), as shown in reaction 3.4. Therefore, the CO2 load-
The adsorption rate of primary amine/secondary amine is fast,
ing of primary and secondary amines may sometimes be
the desorption enthalpy of tertiary amine/stereoamine is low,
slightly higher than 0.5 mol CO2/mol amine.
and its adsorption capacity is high. The advantages of different
R1 R2 NCOO− + H2 O ⇌ R1 R2 NH + HCO3 − (3.4) amines can be harmonized by mixing amine solvent, so as to
produce a new generation of amine CO2 trapping adsorbent.
Tertiary amines do not react directly with CO2, resulting Diamine blends usually introduce some secondary amine into
in carbonic, bicarbonate, and protonated amines. Nitrogen the tertiary amine aqueous solution to obtain the best perfor-
atoms on tertiary amines do not have active hydrogen atoms, mance. For example, compared to using a single MEA, adding
so they do not react directly with CO2 to form zwitterions in a tiny amount of MEA to MDEA’s aqueous solution aids in
the process of absorbing CO2. Instead, they act as alkaline increasing the CO2 absorption rate of MDEA and lowering the
catalysts to promote the hydration reaction of CO2. There- regeneration heat. Additionally, the reaction kinetics and mass
fore, the mechanism of alkali catalyzed hydration occurs. transfer rate also improved with the increase of MEA/MDEA
Theoretically, the CO2 loading can reach 1 mol CO2/mol ratio. Further increasing the number of components that make
up the triamine or tetramine blends helps to maximize the rate the CO2 absorption rate of the solution, improve the cycling
of CO2 absorption/desorption and reduce the heat of regenera- capacity and cycling load, reduce corrosion, and significantly
tion. The comprehensive properties of the multi-component reduce renewable energy consumption.
mixed amine solvent were significantly improved in terms of Liu et al. (2018) introduced the concept of mixed amine
regeneration heat, reaction kinetics, stability, mass transfer, and into non-aqueous solvents and compared its reaction mech-
corrosion problems (Gao et al. 2020). Many screening studies anism in TETA-AMP aqueous solution and non-aqueous
have been conducted on diamine and triamine blends in recent solvent by 13C NMR. Carbamate is formed first, and then
publications (Al Araj et al. 2023; Kandjou et al. 2023; Saghian CO32−/HCO3− is formed during C O2 absorption (Fig. 4).
2− 3−
et al. 2023; Eftaiha et al. 2021). The composition of mixed Thus, CO3 /HCO is desorbed before the carbamate des-
amine absorbents is complex and the reaction mechanism of orption. In contrast, carbamate and C2H5OCO2− form in
CO2 absorption is complex. non-aqueous counterparts.
The two-component mixture was first proposed by After the successful application of two-component mixed
Chakravarty et al. (1985) in order to maximize the potential of solvents, the research direction of three-component and four-
a single amine and make up for the defects of a single amine component mixed solvents is gradually developed. The idea
through binding. Idem et al. (2006) studied in a pilot plant is to combine primary/secondary amine with tertiary amine
and proved that the 4 kmol/m3 MEA—1 kmol/m3 MDEA or steric hindrance amine to make up for the defects of a
(N-methyldiethanolamine) two-component mixed solvent sig- single component by combining the high CO2 absorption
nificantly reduced the regenerative energy compared with the rate of primary amine/secondary amine with the high C O2
5 kmol/m3 MEA single-component absorbent. Other research- loading and excellent regeneration performance of tertiary
ers have also demonstrated that blends of primary/secondary amine or steric hindrance amine, so as to improve the CO2
amine with tertiary amine or steric steric amine can increase capture efficiency of the absorption system.
Fig. 4 NMR spectra of the

CO2-loaded TETA/AMP/
water blended absorbent a in
the absorption step and b in
the desorption step. c The C
O2
absorption/desorption pathways
in aqueous and non-aqueous
solvents. Reprinted with per-
mission from (Liu et al. 2018).
Chemical Society
Non‑aqueous amine solvents is possible for non-hydroamine solvents to minimize energy

use while retaining hydroamine’s capacity to absorb C O2
There are various issues with diluted water for a conven- (Alkhatib et al. 2020). Additionally, lower stripping tempera-
tional water-based amine adsorbent. Energy conservation and tures can lessen corrosion of equipment, amine loss, thermal
regeneration are not made possible by its large heat capac- degradation, and oxidative degradation compared with tra-
ity and high heat of vaporization. Additionally, there is little ditional water solvents (Bihong et al. 2020).
doubt that the water quality has an impact on how quickly Barzagli et al. (2018, 2019) compared the carbon dioxide
equipment corrodes. In recent years, new possible non-aque- absorption characteristics of several aqueous and non-aqueous
ous adsorbents have been the focus of a great deal of study. amine adsorbents. It is thought that 13C nuclear magnetic reso-
Some organic molecules, such as diethylene glycol and EG, nance (NMR) spectroscopy is a useful tool for assessing the dis-
can serve as substitutes for water because they have lower tribution of constituents and the mechanism of reaction in the
heat capacities, enthalpies of evaporation (nearly half that of amine/CO2/solvent system. Figure 5a shows the NMR spectra
water) and peel temperatures. The majority of the regenera- and CO2 loading and C O2 absorption rate of aqueous solvent
tive energy needed to use these non-aqueous amine-based system and non-aqueous solvent system, with red represent-
solvents is used to break down CO2-related compounds, ing aqueous solvent system and blue representing non-aqueous
while the solvent heat and sensible heat of vaporization are solvent system. It can be seen that when reacting with C O2,
considerably reduced because organic diluents have a poor carbamate and bicarbonate are formed in aqueous solution,
heat capacity and enthalpy of evaporation. Consequently, it while only carbamate is formed in organic solution. Therefore,
Fig. 5 a 13C NMR spectra and

the corresponding CO2 absorp-
tion behavior of aqueous and
non-aqueous amine absorbents.
Reprinted with permission
from Barzagli et al. (2018).
Copyright 2018 Elsevier. b The
absorption/desorption cycles of
CO2 in MEA/2ME solutions.
Reprinted with permission from
Guo et al. (2019). Copyright
2019 Elsevier. c The compari-
son of regeneration heat duty in
aqueous and non-aqueous MEA
solutions. Reprinted with per-
mission from Guo et al. (2019).
Copyright 2019 Elsevier. d The
construction and optimization
of functionalized ethylenedi-
amines. Reprinted with permis-
sion from Liu et al. (2019a).
Copyright 2019 Wiley
a higher absorption rate but a lower C O2 loading is obtained little renewable energy (Sharifzadeh et al. 2019). According
in a non-aqueous solution. Compared with aqueous solvents, to the phase state of CO2-rich phase, it can be divided into
non-aqueous solvents exhibit higher desorption efficiency, liquid–liquid and liquid–solid two-phase solvents. It is pos-
larger circulation capacity, lower vaporization heat, and better sible to divide homogeneous adsorbents into two layers as
cycle stability. Figure 5b shows the CO2 absorption/desorp- a result of C
O2 absorption or temperature changes. One of
tion cycle of 5.0 M MEA/2ME (2-methoxyethanol) solution these is the CO2-thin layer, while the other is the CO2-rich
at 313 K. The C O2 absorption behavior and working capacity layer, which holds the majority of the carbon dioxide that
of the solution did not change significantly, indicating that the has been caught. Only C O2-rich phases need to be stripped,
adsorbent remained stable in the cycle test. Figure 5c shows the which is connected to high concentrations of C O2 and low
experimental and relative heat duty of CO2 desorption of three volume flows, thereby reducing sensible heat and heat of
amine systems (5.0 M MEA, aqueous and non-aqueous 2-ME, vaporization, and increasing C O2 pressure. Therefore, the
2-EE (2-ethoxyethanol) under the condition of 313 K within energy saving regeneration process and the reduction of C O2
1 h. It can be seen that using a non-aqueous solvent instead of compression will be realized (Shen et al. 2020).
water can significantly reduce the heat load from 10.8 to about It is important to note that biphasic solvents that are
5.0 MJ kg−1, reducing regenerative energy by 55%. However, loaded with C O2 typically have high viscosities, particu-
it is worth noting that the viscosity of non-aqueous amines larly due to the high concentration of CO2-rich phases.
increases significantly with the loading of CO2. Adding AMP can adjust the high viscosity (Zhou et al.
The rapid increase in viscosity of non-water-based amine 2019). In addition, the rich phase volume ratio and CO2
adsorbents during the absorption of carbon dioxide, which load of mixed amine biphasic solvent are too high, which
worsens mass and liquid transport, is considered a key factor is not conducive to reducing renewable energy consump-
in industrial applications. In order to lessen the viscosity of tion (Wang et al. 2017). Then, the partial substitution of
CO2-supported non-aqueous solutions, Liu et al. (2019a) sug- water with 1-methyl-2-pyrrolidone improved the phase sep-
gested a novel method based upon the correlation of structures. aration performance of the mixed amine biphasic solvent
As CO2-captured nonaqueous solvents, a number of ethylenedi- (Ye et al. 2019). Reducing water content can reduce regen-
amine derivatives were created (Fig. 5d). Good low viscosity eration energy and C O2 capacity, improve phase splitting
and good regeneration were achieved in the range of 50–80 ℃. behavior. A two-stage reaction mechanism involving mixed
Furthermore, using extremely volatile alcohols as organic thin- amine biphasic solvent and CO2 was proposed by Shen
ners often results in significant solvent losses. Similarly, some et al. (2020) (Fig. 6). In the first stage, BDA (1,4-butan-
non-aqueous amine-based solvents have poor regeneration ediamine) reacts with CO2 reactants to produce zwitte-
performance in the absence of N2 scanning. Before applying rion ( BDA + CO2 → BDA+COO−). In the second stage
non-hydroamine solvents to industrial applications, a number there are two pathways, when the concentration of BDA is
of laboratory-scale investigations are required to investigate the high, BDA+COO− reacts with BDA to form carbamate and
noteworthy overall effectiveness of carbon capture. BDAH+ (BDA+COO− + BDA → BDACOO− + BDAH+),
then BDAH+ reacts with DMCA (N,N-dimethylcyclohex-
Biphasic solvents ylamine) to regenerate BDA, and at the same time gener-
ates DMCAH+ (BDAH+ + DMCA → BDA + DMCAH+),
Biphasic solvents have gotten a lot of interest because of this pathway is controlled by kinetics; when the con-
their benefits of having a small extraction volume and using centration of BDA is low, B DA + COO − directly
Fig. 6 A possible two-stage

reaction mechanism between
the mixed-amine biphasic
solvent BDA–DMCA and CO2.
Shen et al. (2020). Copyright
2020 Elsevier
reacts with DMCA to form carbamate and D MCAH +

(BDA+COO− + DMCA → BDACOO− + DMCAH+), this
pathway is controlled by thermodynamics. The reaction
process switches from kinetic absorption control to thermo-
dynamic control as the unreacted amine group is consumed.
It is advised to absorb C O2 at low temperature in the first
stage and high temperature in the second stage.
Due to variations in hydrophilicity, various organic solvents,
including disylane and 1-propyl alcohol, have recently been
found to cause phase splitting of amine absorbents (Wang et al.
2018b; Wang et al. 2019, 2020). Sulfolane specifically facili-
tated the phase separation of MEA liquids during CO2 absorp-
tion, resulting in a hydrophilic C O2-rich phase and a hydro-
phobic CO2-poor phase. Due to the strong interaction between
sulfothane and CO2, the absorption rate of CO2 is accelerated.
In addition, the regenerative energy required for stripping this
CO2-rich phase was limited to 2.67 GJ t−1 CO2.
Solid amine adsorbents
With their high capacity at low regeneration temperature Fig. 7 Promising substitutes for amine-based adsorbents associated
(< 100 ℃), low C O2 partial pressure (10–15%) and less cor- with lower energy consumption for regeneration, including zeolites,
MOF, silica, polymers, graphite/graphene, and clays. Reprinted with
rosive equipment, solid amine adsorbents are effective C O2 permission from Gao et al. (2020). Copyright 2020 Royal Society of
capture substances (Ge et al. 2019). Amino groups and CO2 Chemistry
molecules interact to generate bicarbonate, carbamate, and car-
bamic acid (Sha et al. 2018). The amount of amine, the type of
amine, the density of amine sites, the size of the amine mol- class of amine adsorbents are solid polymer amines, in which
ecules bound on the solid carrier, and most crucially, the par- amines enter the polymer skeleton in covalent bonds such as
tial pressure of CO2 all affect the attributes of adsorbed species (C–C) bonds, which are more stable than Si–O-C bonds (Alesi
(Afonso et al. 2019). The limited heat regeneration capability and Kitchin 2012; Ochiai et al. 2008).
is still a significant drawback given that the adsorption capa- Zelenák et al. (2018) modified SBA-15 using three
bilities of rich amine adsorbents are mostly based on chemical amine silanes, 3-aminopropyl (AP), N-propyl ethylen-
adsorption. Under the influence of adsorbed water molecules, ediamine (DA), and N-propyl diethylenetriamine (TA),
carbon dioxide retention is anticipated to take place. Since and tested the CO 2 adsorption performance at different
then, numerous research teams have prepared amine-based temperatures and partial pressures. The results show that
solid adsorbents by loading amines onto porous substances the adsorption capacity depends on the number of amine
such as zeolites, clays, silica, carbon, polymers, MOFs, and active centers on the surface of the material when the CO2
graphite/graphene to increase their ability to adsorb CO2 fraction is lower than 2 kPa. When the partial pressure
(Fig. 7). However, because of the intricate synthesis and thor- of CO2 is increased, the adsorption capacity of the mate-
ough performance, its industrial use is still very far off. rial may be determined by both physical adsorption and
The commonly used methods for loading organic amines chemical adsorption. Moreover, steric hindrance effect
on porous carriers include (1) impregnation, (2) grafting, and also leads to low utilization rate of amine active sites in
(3) condensation hydrolysis (Wang et al. 2011). The samples adsorbent. Compared with silicon, the conditions for the
obtained by impregnation usually have high carbon dioxide functionalization of amine groups on the surface of car-
adsorption capacity. However, the limited transfer of carbon bon materials are more demanding. At present, the most
dioxide molecules to the active site and the loss of amine after important amination method is the activation of ammonia
many cycles limit the adsorption performance of the adsor- gas to synthesize nitrogen-doped carbon materials for cap-
bent and cannot be recycled for a long time. The problem of turing carbon dioxide (Adelodun et al. 2015).
amine leaching can be solved by attaching amines to the carrier
in the form of covalent bonds, such as hyperbranched amine Alkali carbonate
covalently attached to silicon, amine group functionalization to
silicon or alumina carrier (Wang et al. 2011), adding additives Alkali metal carbonate-based adsorbents (mainly potas-
to polyethylenimine (PEI) to increase its stability. Another sium and sodium carbonate) have been widely studied for
their potential applications in fossil fuel power plants due sodium/potassium carbonate with C O2 and water to achieve
to their low operating temperatures( 50–80 ℃ adsorption the purpose of C O2 removal. The removal of sodium/potas-
and < 200 ℃ desorption), low cost, and high absorption. sium based solid absorbers from flue gas of coal-fired power
plants is mainly achieved through the following two chemi-
Adsorption mechanism cal reactions, where M is Na or K.
Carbonation reaction ∶ M2 CO3 (s) + CO2 (g) + H2 O(g) → 2MHCO3 (s)
The CO2 absorption reaction of sodium/potassium based
solid absorbers mainly involves the gas–solid reaction of
Regeneration reaction ∶ 2MHCO3 (s) → M2 CO3 (s) + CO2 (g) + H2 O(g)
Regeneration of Na2CO3/K2CO3 usually occurs at tem- adsorption and desorption. Depositing adsorbent on metal foil
peratures above 150 ℃ and requires a lot of energy during is one way to solve the heat transfer problem. For example,
this process. In addition, the unmodified N a2CO3/K2CO3 Kondakindi et al. (2013) measured the CO2 adsorption per-
adsorbent has some problems, such as poor durability and formance of N a2CO3/γ-Al2O3 and K 2CO3/γ-Al2O3 coated on
slow carbonation reaction rate, which limit its industrial ferroalloy foils (alloys of iron and nickel) and compared them
application. As a result, carrier materials with high poros- with their powder forms. It is found that the CO2 adsorption
ity, high specific surface area and good adsorption ability capacity of 35 wt % Na2CO3/γ-Al2O3 coating on ferroalloy is
are always used to disperse alkali metal carbonates. At pre- much higher than that of powder form. The various foil sam-
sent, the widely used absorbent carriers include NaX, CaO, ples lost 15% of their capacity during the first 15–20 cycles
SiO2, TiO2, MgO, Al2O3, AC (activated carbon), etc. Among of the durability test, and 40–50% after 500 cycles. How-
them, TiO2, MgO, A l2O3, AC as the carrier of K 2CO3 absor- ever, even after 500 cycles, the CO2 capture performance of
bent has high absorption efficiency and good cycling effect. Na2CO3/γ-Al2O3 coated foils is more economically competi-
Al2O3 supported Na2CO3 adsorbent has good adsorption tive than current methods. In order to improve the adsorption
performance for CO2 at low temperature. Compared with capacity of Na2CO3 for CO2, Yu et al. (2016) synthesized
Na2CO3/Al2O3 adsorbent, adding MgO can improve the a new amine-modified sodium-based adsorbent (NaN) by
adsorption capacity and adsorption rate of CO2. sol–gel method using Na2CO3, 3-amino-propyl triethoxysilane
In terms of carbon dioxide adsorption capacity and adsorp- (APTES), and tetraethylsilicate (TEOS). The new material has
tion kinetics, K 2CO3 is generally superior to N a2CO3. Com- a high adsorption capacity of 2.51 mmol/g, and shows good
pared with sodium-based absorbers, potassium-based absorb- reproducibility and stability during 10 cycles.
ers have fast carbonation reaction rate, high conversion rate, The ability of K 2CO3-based adsorbent to capture C O2
and large absorption capacity. Therefore, most researchers from flue gas was also studied. Zhao et al. (2009) found that
focus on potassium-based absorbers. Although sodium-based the carbonization reactivity of hexagonal K 2CO3 is much
absorbent has a slow carbonation reaction rate and low conver- higher than that of monocline, indicating that the crystal
sion rate, it has attracted the attention and research of many structure has an important effect on the CO2 adsorption
scholars due to its abundant raw material sources, large raw capacity of K 2CO3. Zhao et al. (2010) tested the C O2 cap-
material yield, low regeneration temperature and low cost, ture ability of K2CO3 adsorbent impregnated on Al2O3 in
which reduces process energy consumption. a bubbling-fluidized bed reactor. After 10 cycles, the mor-
The pathway for the Na2CO3 carbonization process was phology of K2CO3/Al2O3 adsorbent changed little, and the
proposed by Cai et al. (2019) (Fig. 8). The experiment shows CO2 capture ability decreased by less than 10%. Lee et al.
that the reaction is controlled by diffusion constraints rather (2014a) studied the thermal stability of K2CO3 adsorbent
than surface reaction dynamics. One of the potential paths for deposited on Z rO2 and T iO2 support in the temperature
rate-limiting reactions is the diffusion of C O2 and H 2O mol- range of 60–150 ℃. Studies have shown that the C O2 capture
ecules through the KHCO3 layer and reaction at the interface capacity of K2CO3/TiO2 decreases rapidly during calcination
of KHCO3 and K2CO3. Another potential reaction paths is the in air (or N2) above 500 ℃ due to the production of inac-
reaction is facilitated by the diffusion of Na from Na+2CO3 and tive K2Ti2O5 and K 2Ti6O13 during calcination. In contrast,
H counter diffusion from NaHCO+3 to their interface. because K2CO3 and ZrO2 can maintain phase without reac-
tion during calcination, K 2CO3/ZrO2 adsorbent still has a
Correlational research good CO2 trapping capacity of about 83 ~ 93 mg C O2/g at
the temperature of 500 ~ 700 ℃.
Due to the exothermic nature of the carbonization process, Wu et al. (2011) studied the failure mechanism of potas-
a method of emitting heat is required to achieve continuous sium based adsorbents ( K2CO3 and K 2CO3/Al2O3) when
Fig. 8 a Scheme of the N

a2CO3
carbonation reaction with sur-
face carbonation and diffusion-
control and (b and c) two
kinds of possible pathways for
Na2CO3 carbonation. Reprinted
with permission from Cai et al.
(2019). Copyright 2019 Ameri-
can Chemical Society
trapping CO2 in flue gas containing SO2. X-ray diffrac- its empty skeleton structure, make it become a typical rep-
tion (XRD) images showed that K HCO3 and K 2SO3 were resentative of porous solid adsorbent materials. With its
formed during the absorption process, and the formation inherent molecular sieve characteristics, rich adjustable pore
of K2SO3 reduced the utilization rate of the adsorbent. The system, high specific surface area, stable hydrothermal sta-
experiment also showed that the presence of water accel- bility and chemical stability, can accurately adjust the pore
erated the K2CO3 acidification reaction. However, after structure and functionalization, and cheap and easy prepara-
pretreatment with water, K2CO3/Al2O3 showed good car- tion of outstanding advantages, zeolite molecular sieve has
bonation and sulfur resistance, which slowed down the fail- become the most deeply studied and widely used gas selec-
ure of the adsorbent. In order to reduce the consumption tive adsorption separation material.
of supported K 2CO3 in the absorption process and improve
its adsorption capacity for C O2, Wu et al. (2014) also syn- Absorption mechanism
thesized cheap calcium-modified K 2CO3 adsorbent. Three
calcium additives, Ca(OH)2, CaO, and C aCO3, were used Studies have found that the absorption mechanism of carbon
to modify K2CO3/γ-Al2O3 samples to test their CO2 cap- dioxide by zeolite molecular sieve is that the linear dipole
ture performance under simulated flue gas conditions. The moment of C O2 forms physical absorption by electrostatic
results showed that Ca(OH)2 was the most effective calcium interaction with metal ions in zeolite, or the strong absorp-
additive. It is worth noting that compared with unmodified tion of carbon dioxide by the formation of carbonate species
K2CO3/γ-Al2O3 samples, K 2CO3/γ-Al2O3 materials modified through double coordination (Wang et al. 2011). There are
by Ca(OH)2 not only show higher CO2 adsorption capacity, three mechanisms for adsorption and separation of zeolites:
but also have better robustness. steric effect, kinetic effect, and equilibrium effect.
Steric effect is mainly applied to the adsorption and sep-
Zeolite molecular sieve aration of zeolites. In this case, only the suitably shaped
molecules are diffused into the adsorbent, while other larger
Zeolite molecular sieve is porous silica aluminate, can exist molecules are sifted out by molecular sieve. The mecha-
naturally, can also be synthetic. The chemical formula of nism of kinetic separation is realized by different diffusion
zeolite molecular sieve is M
x/n[(AlO2)x(SiO2)y]zH2O(where rates of different molecules. Most adsorption and separa-
M is an exchangable cation, y/x is greater than or equal to tion processes are based on the equilibrium adsorption of
1, n is the valence of the cation M, and z is the number the mixture (i.e., CO2 and other gases), which is called the
of water molecules per cell). Zeolite molecular sieve with equilibrium separation process. Steric separation is a unique
mechanism of zeolites due to the special pore size in the smaller than the size of the cage), (ii) one-dimensional chan-
crystal structure. Two typical applications of steric effect nels, and (iii) intersecting channels. Zeolite scaffolds are
are the use of 3A zeolite for drying and dehydration, and 5A generally thought to be rigid, but some studies have shown
zeolite for the separation of n-alkanes from hydrocarbons that they have a degree of flexibility (Ilic and Wettstein
(Boer et al. 2023). 2017; Verbraeken et al. 2021), and that the effects of tem-
When equilibrium separation is not feasible, dynamic perature, cations outside the frame, or adsorbents frame flex-
separation can be considered. Dynamic separation can make ibility on CO2 adsorption have been studied only recently
up for the deficiency of equilibrium separation. Although (Verbraeken et al. 2021; Georgieva et al. 2019, 2021; Grand
the application of dynamic separation is limited, it has great et al. 2020). Flexible frame-shear zeolites exhibit unusual
potential application value. Air separation is a good exam- adsorption isotherms compared to other zeolites due to
ple. In the process of equilibrium separation, the design changes in aperture or window size (also called “breath-
and selection of adsorbents depend on the characteristics of ing”). At 1 bar, the adsorption capacity of these zeolites is
adsorbed molecules: for example, the polarization, dipole similar to that of other pore zeolites (~ 4 mmol g−1), but at
moment, and quadrupole moment of adsorbed molecules. very low pressures (< 0.1 bar), its adsorption capacity will
Zeolite molecular sieve is a kind of adsorbent with high sur- increase sharply, which enables it to obtain higher working
face polarity. If the adsorbed molecule has a high quadrupole capacity even under relatively mild conditions (Georgieva
moment, the surface of the adsorbent needs to have a high et al. 2021; Choi et al. 2020).
electric field gradient. When separating gas molecules with
high dipole moments, it can be an ideal carrier for adsorbent Si/Al ratio The adsorption capacity and selectivity of polar
molecules (Pham et al. 2014). and polarizable molecules in zeolite molecular sieve are
Although zeolite molecular sieve has made some achieve- significantly affected by the Si/Al ratio. The cations out-
ments in the separation of carbon dioxide, and has potential side the frame are usually the active sites for adsorption,
applications in the PSA process, zeolite molecular sieve has and zeolite with low Si/Al ratio has higher Al content, so it
low selectivity for CO2 separation from other gases (N2, has more cations outside the frame, which means that the
CH4, H2O, etc.), and its absorption capacity will be greatly number of adsorption sites per unit mass of materials can be
reduced when the temperature rises above 30 ℃. When the increased by reducing the Si/Al ratio, so as to improve the
temperature is higher than 200 ℃, the absorption capacity adsorption capacity of zeolite for CO2 (Guo et al. 2018b).
of zeolite molecular sieve basically disappears. Aluminate zeolites also contain Lewis bases that can interact
with acidic C O2 molecules. These bases are derived from
Factors affecting CO2 capture the O atom near Al. Therefore, with the increase of Al con-
tent per unit mass of zeolite, the number of base sites will
Type of framework Zeolite skeleton types show several also increase, which means that when Si/Al ratio is low, the
important characteristics of the material, such as the aper- adsorption capacity and selectivity of zeolite for CO2 will be
ture (Å) of the ring and the number of T atoms (T = Si or higher (Wilson and Tezel 2019). However, due to the steric
Al) in the ring, and can be distinguished from one type of hindrance effect of cations, the available pore volume of
zeolite by the size and shape of the channels and cages pre- zeolite is also affected by the Si/Al ratio. Under the condi-
sent within their frames. The minimum pore size allowing tion of low Si/Al ratio, the number of cations per unit mass
CO2 diffusion through is 3.3 Å, which means that rings of of zeolite is more, and its adsorption capacity will be nega-
8MR or larger are required, and smaller rings have too nar- tively affected by the cation steric hindrance. For example,
row apertures. The pore size can be adjusted by the addi- at 5 bar, the adsorption capacity of zeolite LTA with Si/
tion of alkali and alkaline earth metals, thus affecting the Al = 1 is lower than that of zeolite LTA with Si/Al ratio of
mechanism of C O2 adsorption by zeolite. Surface area is 2, 3.5, or 5, due to the reduction of available pore volume.
another property associated with the zeolite skeleton. In Relevant experiments show that the adsorption capacity is
general, zeolites with the same structure and similar crystal significantly affected by the Si/Al ratio under low pressure
size have similar surface areas when they are H-shaped. If conditions. However, at higher pressures, the adsorption iso-
the counter-ion is not H, then the greater the atomic mass therms may converge due to the saturation of the active site,
and size of the counter-ion, the smaller its surface area (Sai and the effect of Si/Al ratio on adsorption capacity is less
Bhargava Reddy et al. 2021). significant (Newsome et al. 2014).
The adsorption performance of zeolite depends on the The hydrothermal stability of zeolite is also affected by
pore topology, pore size, and shape of zeolite, which are Si/Al ratio. Si–O-Al bonds hydrolyze more easily than Si–
important characteristics affecting the diffusion of adsorbed O-Si bonds, and pure silica zeolites are more hydrophobic
matter. The pore topology of zeolites can be divided into than aluminosilicates. Therefore, compared with zeolites
three types: (i) cages separated by Windows (with Windows with low aluminum content, zeolites with low Si/Al ratio
have a larger proportion of readily hydrolyzed bond binding

and higher hydrophilicity, which means that they are less
easily regenerated and have lower hydrothermal stability.
Extra‑framework cations In zeolite molecular sieve, the

cation outside the frame is the acidic point site, the oxygen
atom connected with aluminum atom in the frame is the
basic point site, by using other univalent or polyvalent cat-
ion exchange of cation outside the frame can affect the acid
and base properties of zeolite, and then change the adsorp-
tion behavior of molecular sieve. Because the decrease of
electronegativity of adjacent cations in the zeolite skeleton
will increase the negative charge on the oxygen atom, the
strength of the zeolite basic site increases with the decrease
of the electronegativity of cations. Therefore, the alkalin- Fig. 9 CO2 adsorption isotherm of LiY, NaY, KY, and CsY.
Reprinted with permission from Pirngruber et al. (2010). Copyright
ity strength of zeolite exchanged with alkali metal is as the
2010 Royal Society of Chemistry
order of Cs > Rb > K > Na > Li. The more alkaline zeolite
is, the stronger its interaction with acidic CO2, the higher
its adsorption capacity and selectivity for C O2. However, polarizing power may be to blame, a size exclusion effect
the cationic radius affects the pore size and volume of the is more likely to be the cause (Bacsik et al. 2016). For
zeolite, which may affect the kinetics or the introduction instance, the adsorption capacity of zeolite A is in the fol-
of molecular sieve separation effects, thereby affecting its lowing order: Na > K > Cs. The alteration in pore size can
adsorption properties. In addition, the ability to polarize be primarily blamed for this variation. The effective pore
decreases as the ionic radius increases, which means that window aperture is smaller when zeolite A is partially ion-
cations with larger radii interact less with CO2. Therefore, exchanged with K +. This influences how easily CO2 diffuses
there is a complex balance between alkalinity, polarization into the pores, which accounts for the diminished adsorption
power and spatial effects brought by cation properties out- capacity. However, this effectively blocks the entry of even
side the frame, which together determine the adsorption larger molecules like N 2 or CH4, leading to extremely high
performance of zeolite for C O2, and zeolite type determines selectivity for CO2 adsorption. Zeolite RHO, merlinoite, and
which influence is dominant. chabazite all exhibit comparable tendencies.
The basicity appears to be the dominating determinant
for the adsorption capacity of ion-exchanged zeolites for
the majority of medium- and large-pore zeolites (zeolite X, Metal‑organic frameworks
zeolite Y, zeolite beta, ferrierite), as generally the adsorption
capacity declines in the order K > Na > Li for pressures up to A type of organic–inorganic hybrid material known as
1 bar. However, especially with larger CO2 loadings, acces- metal–organic skeleton material is connected by coordi-
sible pore capacity is important. The cation sizes increase nation bonds between organic ligands, metal clusters, and
in the following order: Li < Na < K < Rb < Cs. As a result, metal ions. Its structure is shown in Fig. 10. It is feasible
when zeolite Na-X is substituted for C s+, the accessible pore to create and synthesize metal organic frameworks MOFs
volume decreases dramatically (from 0.36 to 0.19 cm3 g−1). materials with various structures and types by choosing vari-
As a result, the trend related to basicity is followed for Cs- ous metal ions and organic ligands because of the diversity
exchanged zeolites at low partial pressure of CO2 (p/p0 < 0.1), of metal ions and organic ligands in MOFs materials. High
under which conditions the adsorption capacity decreases in and changeable porosity, extremely high specific surface
the order Cs > K > Na > Li, but at higher CO2 pressure the role area, chemical manipulation, structural variety, and other
of the lower pore volume becomes dominant and the adsorp- benefits can be found in MOFs. They show excellent perfor-
tion capacity of the Cs-exchanged zeolite is no longer the mance in the fields of gas adsorption and separation, proton
highest (Fig. 9) (Pirngruber et al. 2010). Because the available conduction, drug delivery, and so on, especially in the field
pore volume becomes a more crucial factor close to satura- of separation of various gas mixtures with unique selectivity.
tion pressures, the adsorption capacity for the K, Na, and Li
exchanged zeolites may converge and lines may crossover Adsorptive property
around or above 1 bar (Moura et al. 2016).
The adsorption capacity declines in many small-pore MOFs can be divided into rigid MOFs and flexible MOFs
zeolites as the cations’ ionic radius increases. While the according to whether the material structure changes under
The gas affinity can be greatly improved by fixing unsatu-

rated alkali metal sites in MOFs with the tetrazolyl motif
motif (Li et al. 2019b).
The presence of water has a great impact on the C
O2 cap-
ture performance of MOFs. Since water molecules and CO2
will form competitive absorption at the active site of MOFs,
the CO2 absorption performance and selectivity of MOFs
materials will be reduced in the presence of water. Babarao
and Jiang (2009) report that the CO2/CH4 selectivity of rho-
ZMOF decreases by an order of magnitude in the presence
of even 0.1% water vapor in a C O2/CH4 mixture. Yu and
Balbuena (2013) studied the influence of water molecules
on Mg-MOF-74 and found that water molecules would be
linked to the coordination unsaturated metal sites, which
greatly reduced the CO2 absorption performance of Mg-
MOF-74. At the same time, the preparation cost of MOFs
material is expensive, which is not conducive to large-scale
industrial applications.
MOFs have a very high CO2 capture capacity under high
pressure. However, most MOFs have poor CO2 capture
Fig. 10 Schematic illustration of a representative MOF structure, performance compared to other solid physical adsorbents
showing the metal–organic framework structure with building units at lower CO2 partial pressures, and maintaining higher
surrounding a large void space at the center indicated by the large partial pressures is not economically feasible (process unit
yellow sphere. Reprinted with permission from O'Keeffe and Yaghi
(2012). Copyright 2012 American Chemical Society
cost). An economically viable MOF needs to be developed
to efficiently store and separate large quantities of C O 2.
In addition, the synthesis of metal complexes MOF from
external stimuli. Rigid MOFs have strong and relatively organic ligands is in many cases very expensive and the
stable channels. However, flexible MOFs have a soft frame- synthesis process is complex. Due to moisture absorption
work that dynamically responds to stimuli. When certain during CO2 capture, MOFs have durability and mechanical
stimuli are provided by the outside, such as temperature, strength issues. Therefore, the use of MOFs in power plants
pressure, and different guest molecules, the material struc- is limited.
ture changes, so that different guest molecules may exhibit
different opening pressures. Material optimization
Generally speaking, MOFs are superior to zeolites in
terms of working capacity, energy consumption, and effi- ZIFs Zeolite imidazole salt framework (ZIF) is composed
ciency. Their properties can be further improved by modifi- of M-Im-M, where M represents Zn or Co cation, Im rep-
cation after synthesis, functionalization of organic linkers, resents imidazole salt connector, which is a subfamily of
and doping of nanomaterials in the skeleton (Olajire 2018; MOF (Chen et al. 2014a). The structure of ZIF molecular
Ramos-Fernandez et al. 2018). Through the rapid heat treat- sieve is diverse and similar to traditional aluminosilicate
ment after synthesis, the stronger interaction between C O2 molecular sieve. ZIF possesses the properties of MOFs and
molecules and MOF was realized, thus greatly improving zeolite at the same time, combining the advantages of MOFs
the adsorption performance. The strengthening of the lattice and zeolite, such as high crystallinity, ultra-high surface
is confirmed by temperature-activated transmission (Babu area and special chemical and thermal stability, which has
et al. 2019). The introduction of tertiary amine linkers pro- broad application prospects in the field of gas separation
duces a higher affinity for carbon dioxide, thus improving the and storage.
overall adsorption capacity of carbon dioxide (Gottschling ZIFs demonstrate higher selectivity for C O2 in flue gas
et al. 2019). Fewer polar or non-polar solvents are more con- than MOFs and ultimately rely on their unique interactions
ducive to the entry of alkylamines into MOFs than more with CO2 molecules to function as selective CO2 adsorbents
polar solvents. Alkylamine molecules dispersed in solvents (Kumar et al. 2020). Figure 11 describes the theoretical
with lower polarity have higher chemical potential, which results of CO2 adsorption by different groups of ZIF adsor-
promotes the integration of more alkylamine molecules into bents, along with the calculated results of changes in dipole
the skeleton and thus forms modified MOFs, thus greatly moments, interaction energy and charge density of different
improving the C O2 capture performance (Li et al. 2019a). CO2@ZIF forms. The CO2 capture capacity depends on the
Fig. 11 Optimized geometries

of the different CO2@ZIFs
complexes where the C O2
molecule is trapped in the cavity
center of each ZIF structure.
Izzaouihda et al. (2017). Copy-
right 2017 American Chemical
Society
shape and size of the pore where the gas molecules have magnesium 2,5-dihydroxyterephthalate (Mg-MOF-74) led
been trapped, and this study showed a strong association to improve C O2 adsorption capacity under humid and dry
between CO2 adsorption energy and the ZIFs cavities vol- circumstances. Since polyamines provide additional binding
ume. A combination hydrogen-like bonding and -stacking sites, the functionalized amino-Mg-MOF-74 (TEPA-MOF)
interaction is what the physisorption mechanism that regu- had a higher C O2 adsorption capacity of up to 26.9 wt%
lates carbon dioxide capture anticipates. Additionally, the compared to 23.4 wt% of the original MOF. Additionally,
geometry of C O2 is unaffected by adsorption, but in other it has been demonstrated that amino-MIL-53 has a higher
ZIFs, it induces a significant structural variation (Izzaouihda separating factor for separating CO2 and CH4 (Arstad et al.
et al. 2017). 2008). Prior research typically used a single solvent to syn-
thesize amino-MIL-53 (Boutin et al. 2011). But because
Chemically modified MOFs material Good modifability is using a single solvent results in limited C O2 adsorption
one of the major advantages of MOFs materials. The prop- (48 cc g−1 at 273 K), co-solvent strategies can be used to
erties and structure of MOF materials can be adjusted by increase CO2 collection.
impregnating the internal surface or adding active groups In order to manipulate the micropore structure, improve
such as polyalkyl amine, so as to improve the gas adsorp- the absorption capacity and selective adsorption of CO2 in
tion performance of MOF materials. Many amine-modified the N2/CO2 mixture under ambient pressure, Hussein Rasool
MOFs materials have been created in this area. Su et al. Abid et al. (2018) synthesized amino-MIL-53 using meth-
(2017) reported that the functional level of amine had a sig- anol, ethanol, methanol/acetic acid or ethanol/acetic acid
nificant effect on improving the adsorption of C O2 since mixture and DMF as co-solvents. The BET surface area of
the best surface coverage might result in increased stabil- amino-MIL-53-DMA (methanol/acetic acid with dimeth-
ity and performance under both C O2/H2O co-adsorption ylformamide) was the largest at 632 m2 g−1, and its CO2
and pure CO2. Additionally, optimum C O2 capacity could adsorption capabilities were the strongest at 75 cc g−1. These
be attained under dry or wet circumstances with partially extremely valuable studies imply that MOFs functionalized
saturated surface coverage thanks to a synergistic bind- with amines have exceptional CO2 adsorption and separa-
ing of amines and CO2 to the metal centers. Tetraethyl- tion characteristics and tremendous prospective uses in the
enepentamine (TEPA) post-synthetic functionalization of environment and energy sectors.
MOF‑composite materials In general, MOFs have some are widely used in energy conversion and hydrogen produc-
limitations that limit their uses, including as moisture sen- tion products in the whole coal gasification combined cycle
sitivity and poor thermal and chemical stability. However, power generation system.
by combining MOFs with other active species, including as As a solid adsorbent, carbon-based CO2 adsorbents fre-
graphene oxide, carbon nanotubes, metal nanoparticles, and quently rely on physical adsorption mechanisms or a tenu-
organic polymers, these drawbacks can be solved. ous link between the C O2 and the adsorbent surface, which
Research on composite materials made of MOFs and reduces regeneration energy. Carbonitride, carbon nanotube,
immobilized nanoparticles (NP@MOFs) is a rapidly graphene, carbon molecular sieve, and activated carbon are
expanding field. The unique functionality and adaptability the principal carbon-based adsorbents. Among these, bio-
is provided by the combination of MOFs’ high surface area, mass carbon, which is also the most fundamental carbon
high porosity, and good modifiability. Due to its acidity, material, is mostly used to prepare activated carbon.
CO2 is predicted to bind to the potently basic sites of metal However, due to the physical adsorption of carbon mate-
oxides, such as MgO, ZnO, etc. MO reacts with C O2 to form rial absorbers in the process of C
O2 absorption, the absorp-
carbonate, which may then be heated to regenerate into pure tion temperature is low and sensitive to temperature, and the
CO2. Chang et al. (2020) developed a MO-decorated ZIF-8 selection of absorption is poor, so the use of carbon mate-
(MO@ZIF) composite for C O2 regeneration and adsorp- rials is limited. At present, the main research objective is
tion. Because N atoms in the ligand mIm are present in to enhance the adsorbent-adsorbent interaction energy and
the framework, ZIF-8 was employed as the scaffold to sup- improve the selectivity of CO2 absorption. At present, there
port and disseminate MO, which was also favorable to C O2 are three methods: (1) adjusting the carbon’s structural char-
adsorption. MgO-doped ZIF-8 (MgO@ZIF-8) was discov- acteristics, (2) chemically altering the carbon surface, and
ered to have MgO NPs nanoconfinement in ZIF-8 regardless (3) preparing carbon-based hybrid composites to enhance
of MgO concentration, and with a greater CO2 adsorption the efficiency of carbon-based CO2 capture (Fig. 12).
of 1.227 mmol g−1 at ambient temperature, 1 bar. Finally,
successful MgO nanoconfinement in ZIF-8 results in a sig- Biomass‑based carbon
nificant reduction in carbonate decomposition temperature.
The study suggests approaches for combining physical and Activated carbon (AC) and inexpensive pyrogenic carbon
chemical sorbents for improved CCUS capacity, as well as are the two fundamental carbon compounds frequently
tactics for reducing the energy penalty associated with sorb- employed for CO2 extraction. Additionally, its surface area
ent renewal. and pore structure can be enhanced by further modifying
By growing MOFs on the surface or inside the pores AC, or by adding metal oxide, amino and other basic groups
of other materials, MOF composites can also be created. to the surface, which will increase its ability to adsorb sub-
Because several 2D materials can have their surfaces func- stances (Chiang and Juang 2017).
tionalized and commonly have a variety of reactive func- Low-cost pyrogen carbon materials mainly include agri-
tional groups, they can be employed as substrates for the cultural carbon, biochar, charcoal, carbonized biomass, etc.
formation of MOF composites (Ding et al. 2019). Several Due to its rich surface functional groups and high specific
graphene/M-MOF-74 composites, MCGr-X (M = Mg2 + , surface area, it can absorb heavy metals and other pollut-
Ni2 + , or Co2 + , X = 0, 2, 5, and 10 wt%), with benzoic ants, and has been widely used in carbon sequestration and
acid functionalization were created. The graphene basal environmental remediation fields. It has similar properties
planes served as supports to strengthen the MOF matrices in and adsorption mechanism to C O2 adsorption, making it an
these materials (Kumar et al. 2016). It is interesting to note ideal material for CO2 capture (Creamer and Gao 2016).
that each MCGr-X compound has a higher C O2 adsorption Carbon-based materials tend to have very small pores before
capacity than the corresponding pristine MOF. The most they are subjected to pyrolysis or gasification. Adsorption in
striking example was MgCGr-10, which at 1 atm and 298 K this situation is based on activated diffusion, where the gas
absorbed 8.1 mmol g−1 CO2. needs activation energy to diffuse. Following pyrolysis, the
pore diameter rises and sorption is guided by the principles
of Knudsen (or bulk) diffusion. Here, diffusion into and out
Carbon‑based material of a feeder pore system of larger pores (i.e., mesopores) lim-
its the pace of gas transport (Liaw and Wu 2015).
As a C O2 absorbent, carbon material is one of the most Pyrogenic biomass has recently been discovered to be
promising absorbent materials. Carbon materials have many effective at capturing C O2. For the purpose of creating
advantages, such as cheap and easily available raw materi- porous carbons for CO2 capture, many types of biomass,
als, large specific surface area, high porosity, high plasticity including rice husk, crab shell, sawdust, coconut shell, and
of surface functional groups, easy regeneration, etc., and poplar anthers, have been investigated (Yang et al. 2017).
Fig. 12 Different methods to

improve the performance of
carbon-based CO2 adsorbents.
Gao et al. (2020). Copyright
2020 Royal Society of Chem-
istry
Additionally, research has shown that physical adsorption dipole–dipole interactions. It is anticipated that adding
is the primary mechanism by which C O2 is captured in bio- Lewis bases or heteroatoms like nitrogen that are electron-
genic pyrolytic carbon (also known as biochar), highlighting rich may improve the ability of these materials to capture
the significance of high surface area on sorption capacity CO2. Since most activated carbons create oxygen surface
(Hao et al. 2013). The adsorption of CO2 onto biochar was groups with an acidic nature, surface oxidation imparts
evaluated by Creamer et al. (2014) using a series of car- electron acceptor qualities to the carbon surface (Chiang
bonization temperatures. At 300, 450, and 600 ℃, sugar- and Juang 2017). Rao et al. (2019) prepared N-rich porous
cane bagasse (BG) and hickory wood (HW) feedstock were carbon by single-step sodium amide activation of carbon-
transformed into biochar. The maximum CO2 capture capa- ized water horn shell at 400–500 ℃. The optimal CO 2
bility was found in biochar made from sugarcane bagasse absorbents at atmospheric pressure were 4.50 mmol g−1 at
feedstock at 600 ℃ (73.55 mg g−1 at 25 ℃ and 101 kPa). 25 ℃ and 6.04 mmol g−1 at 0 ℃, respectively. The sample
For the bagasse- and hickory-based biochar, respectively, the also shows steady cycle capacity, quick CO2 adsorption
feedstock was still able to collect 38.72 and 34 mg g−1 even rate, low CO2 adsorption heat, high selectivity for CO2/N2,
after being pyrolyzed at 300 ℃. Surface area was a key factor and strong dynamic CO2 absorption. The efficacy of these
in the CO2 adsorption process, according to experimental adsorbents for CO2 adsorption is significantly influenced
findings, which indicate that CO2 was weakly attached to the by pore size distribution in addition to the well-known
surface of the biochar through physisorption. variables of narrow pore volume and N content.
De Souza et al. (2020) studied the changes of specific In conclusion, the virgin biomass carbon’s poor poros-
surface area and porosity of carbon materials after the ity restricts its applicability in C
O2 adsorption applica-
chemical activation of KOH and the physical activation of tions. However, high-temperature pyrolysis and physical
CO2, and analyzed its influence on CO2 adsorption. Using or chemical activation of biomass carbon can be used to
acai (a species of South American palm) as a precursor for increase the porosity and specific surface area, producing
carbonization at 600 ℃, they synthesized a porous carbon carbon with a high C O2 capture capability. Despite recent
material with adjustable porosity and degree of graphitiza- papers on CO2 capture, there are still a few open questions
tion, whose porosity is regulated by KOH or CO2 activation. that require investigation. Future research should focus on
The results show that compared with C O2 activation, KOH developing adsorbents with high C O2 adsorption at varied
activated carbon materials has larger porosity, so the KOH temperatures and pressures.
activated material has the best CO2 adsorption performance,
and the number of ultrafine pores significantly affects its Carbon nanotubes
adsorption performance. Under the conditions of 0 ℃ and
1 bar, the adsorption surface area of activated carbon is Carbon nanotubes (CNTs) are a class of carbon materi-
3250 m2 g−1, and the adsorption capacity of CO2 can reach als that have a wide range of uses because of their spe-
6.1 mmol g−1.The embedding of metal potassium in the cial characteristics, including topological hollow tubular
carbon layer and the subsequent further reaction are the shapes, chemical and thermal stability, and huge pores.
mechanisms by which KOH activation fully develops the Single-walled carbon nanotubes (SWCNTs) and multi-
micropore structure. This indicates that chemical activa- walled carbon nanotubes (MWCNTs) are the two catego-
tion is more conducive to the pore control of carbon-based ries into which CNTs can be divided. Figure 13 provides
materials, and thus affects the capture of CO2. a schematic illustration of the many forms of CNTs. An
Since CO2 is a weak Lewis acid, the addition of basic adsorption enthalpy of 2.3 kJ mol−1 was produced by the
surface groups can enhance the interactions between AC physical adsorption of C O2 on pure single-walled carbon
and C O 2 , including H–H bonds, covalent bonds, and nanotubes (SWCNTs). In comparison to activated carbon
and horn-shaped CNTs, the comparable CO2 uptake was desorption CO2. Deng and Park (2019) reported a biomolecu-
roughly 4 mmol g−1 (Sawant et al. 2012). lar inspired amine-coiled carbon nanotube design in which PEI
Due to their distinctive physical and chemical charac- chains spirally wrap each carbon nanotube and are decorated
teristics, such as strong thermal stability and chemical with a bunch of amine-carrying spacers that help to wrap and
stability, amine-functionalized carbon nanotubes (CNTS) create additional adsorption space between the CNT and PEI
have gained increasing attention for trapping CO2 in flue chains. Both PEI and spacers aid in carbon dioxide capture.
gas. Numerous investigations have demonstrated the supe- The outcomes demonstrated that the CO2 capture capacity
rior CO2 adsorption capacity of multi-walled or single- could be increased to 3.875 mmol g−1 by using the isolator
walled carbon nanotubes that have been functionalized with the best molecular length and amount of amino acids.
with amines. According to Bae et al. (2007), hydrogen Additionally, PEI-purine-CNT maintain their adsorption capa-
bonds and weak electrostatic interactions were responsible bility after 50 cycles of sorption–desorption, indicating that
for the interaction between CNTs and polyethylenimine they have a significant potential for stable and cyclic carbon
(PEI). Under standard experimental circumstances, they absorption from the chimney and air.
found that the connection was spontaneous and stable.
Keller et al. (2018) reported a highly porous multi-walled Carbon nitrides
carbon nanotube (MWCNT) microtubule with high inter-
nal surface area functionalized with PEI by wet impregna- Carbon nitride (CN) is a two-dimensional material consist-
tion. The tubular structure provides more design flexibility ing only of carbon and nitrogen atoms connected by strong
for managing the distribution and residence time of gases. covalent bonds. It has been used as a metal-free and visible
Microtubules’ high specific surface area and porosity were light active photocatalyst due to its excellent photoelectric
sustained when PEI content in the impregnation solution and physico-chemical properties, which include low cost,
was low, and CO2 absorption increased as PEI content did. high chemical and mechanical stability, adjustable band
These microtubules are extensively employed in the CO2 position, customized surface function, suitable band gap,
extraction process because PEI adsorbent and the CNTs and metal-free properties (Talapaneni et al. 2020; Maeda
matrix are both thermally and chemically stable. et al. 2014). These materials’ significant potential as C O2
Liu et al. (2014) prepared carbon nanotubes impregnated adsorbents has recently been highlighted by the processing
with tetraethylglutenediamine (TEPA) as solid-phase amine of them into highly developed porous nanostructures with
adsorbent for CO2 capture. The maximal capacity for adsorp- particular shape, high specific surface area (SSAs), and rich
tion of 2 v% C O2 and 2 v% H 2O at 40 ℃ is approximately basic functional group content. The presence of NH2 groups
3.87 mmol g−1. Alkaline hydroxides (like KOH and NaOH) in the skeleton of CN, a nitrogen-rich substance, is vital
can also be used as activators to improve the surface area and since it gives the substance its basic features and determines
porosity of MWCNTs. TEPA was fixed to modified carbon its potential as a good CO2 adsorption material. The next
nanotubes by Irani et al. (2017) to create CO2 adsorbent. Under generation of adsorbents for carbon dioxide capture could
the circumstances of 10 vol% CO2 and 1 vol% H 2O at 60 ℃, be provided by this unique characteristic in conjunction with
the adsorption capacity of C O2 reached 5 mmol C O2/g when the highly porous structure. Due to Lewis base’s porous
the optimal TEPA loading of modified carbon nanotubes structure and large specific surface area, it is anticipated
(MCNTs) was 75 wt%. Low activation energy, high desorp- that CN with varying nitrogen contents and defect sites will
tion rate, and inexpensive capture characterize MCNTs/TEPA exhibit good CO2 adsorption behavior.
Fig. 13 Schematic representa-

tion of single- and multi-walled
carbon nanotubes. Reprinted
with permission from Hosned-
lova et al. (2019). Copyright
2019 Wiley
Bulk graphitized CN has a low specific surface area, single, double, and multiple layers in graphene. Monolayer
which results in essentially negligible reactivity to the graphene is a single layer of hexagonal carbon sheets that are
adsorption of C O2. The development of CN into compos- arranged in two dimensions. Bilayer graphene has two lay-
ites or hybrid nanostructures to absorb carbon dioxide was ers, whereas hexagonal carbon sheets often have three to ten
a major focus of earlier research. For instance, Peng et al. layers. The graphene has some distinctive qualities, such as
(2018) reported an amine functionalized g-C3N4 adsorbent high theoretical surface area of 2630 m2 g−1, natural mobil-
by physical impregnation of polyethylenimide (PEI), which ity of high charge of 2 × 105, strong Young’s modulus of 1.0
possesses several amine groups and has very low volatil- TPa, outstanding thermal conductivity of 5 × 103 W m−1 K−1
ity. The trapping performance of g-C3N4 (including trap- and high transparency (~ 97.7%). This type of graphene has
ping capacity and trapping selectivity) was dramatically been extensively used in a variety of disciplines, includ-
enhanced following the amine functionalization process. At ing optical power limitation, the removal of heavy metals,
100 ℃ and atmospheric pressure, the PEI-g-C3N4 composite supercapacitors, sensors, fuel cells, batteries, solar cells, the
had a maximum CO2 capacity of 3.77 mmol g−1. It is impor- degradation of organic contaminants and other fields (Ramar
tant to note that the adsorption of CO2 is only caused by the and Balasubramanian 2021, 2020; Ramar and Karthikeyan
presence of amine groups on the surface of the composite 2021). Graphene-based adsorbents have been the subject of
nanostructure and is unaffected by the specific surface area substantial research for CO2 adsorption due to the high spe-
of the nanostructure. cific surface area of graphene materials and their compara-
Mesoporous carbon nitride (MCN) has also been tively inexpensive cost in comparison to other carbon-based
researched due to its distinct pore structure and adjustable adsorbents.
nitrogen-containing functional groups. In order to improve Mishra and Ramaprabhu (2012) achieved functional mod-
nitrogen content and carbon dioxide adsorption capacity, ifications on graphene surfaces by optimizing the interlayer
Park et al. (2017) synthesized MCN materials with high structure of graphene with O-containing functional groups
nitrogen content and adjustable pore size using 3-amino- and organic/inorganic complex hydroxyl groups. Addition-
1,2, 4-triazole as CN precursor and KIT-6 silica as nano ally, chemically altering the graphene surface may result in
hard template. MCN-8E-150 has a maximum C O2 adsorp- a loss of surface O atoms, significantly lowering the mate-
tion capacity of 5.63 mmol g−1 at 273 K and 30 bar. MCN- rial's thermal and structural stability. Meng and Park (2012)
8E-150 is a material that may be recycled for C O2 collec- developed an efficient CO2 capture material for process-
tion without structural collapse or deformation. It has a high ing graphene nanoplates modified with graphene oxide at
specific surface area (232 m2 g−1), a good ordered meso- 423 ~ 673 K under vacuum conditions. The results showed
scopic and graphite structure, a low C/N ratio, and a high that the maximum CO2 adsorption capacity of functionalized
nitrogen content (higher –NH or –NH2 group). It has also adsorbent was 56.4 mmol/g at 298 K and 30 bar. The huge
been reported that large-scale CNs can be patterned into layer spacing and pore volume of graphene are indicators
mesoporous structures for the capture of C O2 under high of its significant adsorption capacity. Zhang et al. (2012)
pressure. The next generation of carbon dioxide adsorbents synthesized a material with a maximum specific surface area
may be formed thanks to the intriguing electrical character- of 3100 m2/g by chemical activation of graphene oxide using
istics of CN. KOH microwave and thermal stripping.
In summary, the unique chemical characteristics and
molecular framework structure between C and N of CN Carbon nanofibers Carbon nanofiber (CNF) is a polymer
material allow it to chemically mix with other catalytically fiber (polyacrylonitrile, phenolic resin, polyethylene, etc.),
active compounds or physically adsorb CO2. It is still a long cellulose and asphalt as the precursor carbonized interme-
way off from creating effective carbon nanostructures for diate products. As a result, carbon nanofiber retains the
CO2 collection. physical and chemical properties associated with their pre-
cursors. For example, high tensile strength and elasticity.
Other types of carbon‑based materials The degree of graphitization after carbonization is higher
than that of activated carbon. Similarly, carbon nanofiber is
Graphene At the University of Manchester in 2004, Geim highly resistant to corrosion. Its specific surface area is about
and Novaselov made the initial discovery of graphene, a 1000 m2/g to 2000 m2/g. Carbon nanofiber has the following
brand-new member of the family of carbon nanostructures. advantages: First, carbon nanofiber has a relatively narrow
They used scotch tape to split the graphite into its constituent and uniform pore size distribution, which also enables it to
layers. Carbon atoms in graphene are linked by s p2-bonds interact with adsorbent. Secondly, compared with activated
and have flat sheets that are one atom thick. These sheets carbon, carbon nanofiber has a smaller and more uniform
are joined to one another in a closely packed honeycomb pore size, which can accelerate adsorption and desorption
lattice by σ and π bonds. Carbon atoms are arranged in rates. Finally, during the carbonization process, it retains the
characteristics of graphitization, so that carbon nanofiber adsorbent using chemical vapor deposition technology. By
has high strength and good elasticity, which gives it good adding CH4 to the surface of CMS, they created a new CMS
conductivity, heat resistance and plasticity. adsorbent CMS6. At 0 ℃, 1 bar, CMS6 had the maximum
Hong et al. (2014) developed a porous CNF for C O2 cap- rate of C
O2 absorption of 1.73 mmol/g. This plan offers a
ture using electrospinning polyvinylidene fluoride (PVDF) fresh approach for changing CMS CO2 adsorbent, and the
as raw material. At 303 K and 1 atm, the CO2 adsorption result is impressive.
capacity was at its greatest, measuring 3.1 mol/kg. The pro-
duced PVDF-based CNF is a potential adsorbent for C O2
capture since it also possesses quick adsorption–desorption
kinetics and strong recyclability. Li et al. (2016) studied the Medium temperature CO2 absorbent
CO2 capture performance of N-doped CNFs. Their adsorp-
tion capacity reached 6.44 mmol/g at 273 K and 1 bar. Addi- Layered double hydroxides
tionally, they proposed a potential mechanism for how Lewis
bases interact with hydrogen bonds. Iqbal et al. (2017) syn- Layered dihydroxides (LDHs) with finely regulated chemical
thesized amine-functionalized CNFs that could capture C O2 compositions and customizable characteristics have received
efficiently by means of CNT doping. At 298 K and 1 bar, the much research in a variety of sectors. Despite being utilized
greatest CO2 absorption rate was 6.3 mmol/g. More impor- as adsorbents for many years, LDHs were only used for the
tantly, the flexible material is well suited for CO2 capture due first time in carbon dioxide capture in 2001. Mixed oxides
to its high mechanical strength and robust porous structure, derived from LDH are considered to be important mesother-
which overcome the drawbacks of solid adsorbent structure mal carbon dioxide capture materials.
collapse and simple crushing.
Performance of absorption
Carbon molecular sieve Research on carbon molecular sieve
(CMS or MSC) began in the 1970s. Carbon molecular sieve Layered double hydroxides (LDHs), which are anionic clays
is similar to activated carbon fiber with smaller pore size. with layered structures, are shown in Fig. 14. Because of
Currently, carbon molecular sieves have been successfully its special layered structure and physicochemical proper-
used to separate nitrogen from air. The principle is to sepa- ties, it has been widely used in ion exchange, adsorbent
rate gas mixtures according to the different dynamic diam- and catalysis in recent years. Its basic structural formula is
eters of each gas molecule in the air. When the kinetic diam- [M2+1-xM3+x(OH)2][An−]x/n·zH2O, where M2+ and M3+ rep-
eter of the separated gas is greater than or equal to the pore resent divalent (Zn2+, Mg2+, Ni2+, etc.) and trivalent cation
size of the carbon molecular sieve, according to its screening (Fe3+, Al3+, Mn3+, Ga3+, etc.), respectively. An− represents
effect, the separated gas molecules are separated from the the N-valent anion ( Cl−, CO32−, SO42−, etc.), the x value is
pores that cannot pass through the carbon molecular sieve, usually between 0.2 and 0.4.
so they are screened (Sun et al. 2019). In the preparation Generally, the mixed oxides derived from LDH gener-
process of carbon molecular sieve, coal or charcoal with ally have a large number of basic sites and high specific
uneven structure is usually used as raw material. Therefore, surface area, and can absorb acidic gas C O2 at 200–400 ℃.
it is difficult to obtain uniform pore size in carbon molecu- The intermediate temperature carbon dioxide absorbent
lar sieve. At the same time, there are various groups on the derived from LDH has potential applications in the process
surface of carbon zeolite, which also brings some challenges of absorbing enhanced water–gas conversion reaction and
to the modification of carbon zeolite. biomass reforming. LDH itself has no alkaline sites, while
Alcañiz-Monge et al. (2011) studied the C O2 absorption the heat-treated metal oxides have a lot of alkaline sites
on the surface of granular and monolithic CMS adsorbents in them. The active site for C O2 adsorption is Mg-O spe-
and examined the impact of pore plugging. The results dem- cies, according to the C O2 adsorption mechanism of LDH
onstrated that carbonizing CMS surface molecules caused adsorbent. Gao et al. (2013) proposed two possible mecha-
them to break into particles with smaller pores, resulting nisms for the formation of LDH activity Mg-O. Mg-o is
in pores that were compatible with C O2 elements. Fathi obtained by creating Mg vacancies by replacing M g2+ with
3+
and Asgari (2020) studied the adsorption performance of Al at the octahedral site of the MgO lattice, or by diffus-
SAPO-34 molecular sieve adsorbent. Ion exchange in the ing Al3+ out of the octahedral magnesite layer and leav-
combination of C O2 and C H4 improves the Si/Al ratio and ing Al vacancies. In-situ approaches were recently used by
pore size, enhancing the adsorption selectivity and effi- Zhu et al. (2019a) to clarify the C O2 adsorption process of
ciency. At ideal conditions of 290.5 K and 4.6 bar, SAPO- K-promoted MgxAl-CO3 LDH at various Mg/Al ratios. They
34 had a C O2 absorption capacity of 1.5 mmol/g. Morali demonstrated a synergistic effect between Mg/Al ratios and
et al. (2019) achieved functional modification of CMS C O2 K ions. After adsorption of C O2, didentate carbonate was
Fig. 14 Schematic structure

of the LDHs. Reprinted with
permission from Yong et al.
(2001). Copyright 2001 Ameri-
can Chemical Society
formed on the K-promoted LDH surface. However, a single Using urea hydrolysis method, Qiao et al. (2015) prepared
carbonate with a potent binding force can occur when the multilayer LDH/MgCO3 compounds on aluminum foil/
Mg/Al ratio is less than 2. The exact mechanism of C O2 grid. When using aluminum foil mesh as the only source of
adsorption and desorption by LDHs is intricate in practice. substrate and aluminum, sintering and paste issues can be
LDH can be prepared by coprecipitation method, urea efficiently avoided. Additionally, for use in practical appli-
decomposition method, structure reconstruction method, cations, aluminum-supported LDH sheets can be further
sol–gel method, ion exchange method, and reverse-phase manufactured into any shape.
microemulsion method. Among them, a uniform LDH with Another efficient way to increase LDH’s ability to capture
a wide particle size range (10 nm to 1 pm) and low crystal- CO2 is by doping it with alkali metal carbonate. Numerous
linity is usually obtained by coprecipitation, which is more research have concentrated on the use of K2CO3 as an accel-
favorable for selective anion stripping and exchange embed- erator because it can increase the number of active sites on
ding. On the contrary, the LDH of carbonic acid intercala- LDH and consequently improve its adsorption capacity, ther-
tion is typically produced through the urea hydrolysis pro- mal stability, and cycling stability. The amount of K 2CO3
cess, which has a large size (micron scale), high crystallinity doping on LDH determines the adsorption level. Then,
and purity (Yu et al. 2015, 2017). In order to improve the 10–30 wt% K2CO3 was found to be the ideal load because
crystallinity and control the morphology of LDH, hydro- too much K2CO3 could block the LDH's pores. According
thermal treatment, ultrasonic degradation, and microwave- to Kim et al.’s research (Kim et al. 2016b), organic sol-
assisted method are generally used in the aging process. vents diffused K2CO3 during K impregnation more effec-
tively than inorganic solvents, which improved the ability
Material optimization to promote C O2 capture. Widening the interlayer gap and
encouraging more cation exchange on the outer or inner sur-
LDH matrix composites have emerged in recent years as face of each layer are both possible effects of long carbon
highly promising C O2 adsorbent materials. Different carbon chains acting as anions. In light of this, at 300 ℃, the C O2
materials (CNF, GO, and CNT) were investigated as the car- absorption rate of stearate column LDH driven by K 2CO3 is
rier of LDH adsorbent in order to increase the adsorption 1.93 mmol g−1, which is much greater than that of carbon-
capacity and cycling stability of LDH adsorbent. Electro- ate intercalation LDH promoted by K2CO3 (1.11 mmol g−1).
static self-assembly, direct coprecipitation, and hydrother- Meis et al. (2010) examined the performance of loaded and
mal urea reaction are the three most often utilized synthesis unloaded LDH that had been doped with K2CO3 for CO2
techniques. Garcia-Gallastegui et al. (2012) prepared LDH/ adsorption. They discovered that loaded LDH had a greater
MWCNT and LDH/GO composites by direct coprecipitation K2CO3 adsorption capacity than unloaded LDH, which was
method. The interaction between the gas and the adsorbent caused by the presence of K + on its surface following heat
is improved as a result of the rise in effective SSA and the treatment. Upon loading K 2CO3, K+ displaces M g2+ in the
disordered structure of the composite, which improves the LDH and allows more oxygen atoms in its vicinity to absorb
CO2 capture performance of LDH in terms of cycle stabil- CO2. As shown in Fig. 15, after loading K2CO3, unsupported
ity and adsorption capacity. Using an electrostatic driven LDH added two reactive oxygen sites and supported LDH
self-assembly technique, Wang et al. (2015) created highly added one reactive oxygen site. For CO2 capture, the high
dispersed LDH/GO composites from two stripped GO and frequency of low coordination locations (corners and edges)
LDH solutions. Due to the exfoliating LDH dispersion and is thought to be important.
the stabilizing action of GO, the LDH/GO composite had Commercially available LDHs frequently have stacked
the maximum CO2 absorption rate when the GO content structures that resemble stones and have low SSA when
was 6.54 wt%, which was double that of pure LDH alone. doped with alkali metal ions. Despite reports that LDH
layers can be peeled into nanosheets using “top-down” Absorption mechanism

or “bottom-up” techniques, their high surface charge and
hydrophilicity make them simple to reassemble during The reaction of CO2 with MgO produces stable MgCO3
drying. By adopting the straightforward peeling technique (ΔH≈1100 kJ mol−1). MgO absorbs carbon dioxide at tem-
known as AMOST, Chen et al. (2014b) developed a number peratures ranging from 200 to 400 °C and can be easily
of Zn-Al LDH nanosheets with high SSA (459 m2 g−1) and regenerated at moderate temperatures of 450 °C. Compared
large pore volume (2.15 cm3 g−1). AMOST describes the with CaO based absorbent, its regeneration temperature is
step in the co-precipitation process where LDH wet cake lower and the energy consumption required during regen-
is washed with AMO solvent. The water between the two eration is also lower. However, pure MgO has a medium
layers is eliminated in this manner. The substituted AMO CO2 absorption capacity and poor absorption kinetics. It is
solvent molecules are expelled during the subsequent drying easy to agglomerate in the regeneration process, resulting
procedure, which makes it simple for the LDH layer to slide. in a decrease of specific surface area. Therefore, MgO, as
Zhu et al. (2019b) washed the flower-like Mg3Al-CO3 LDH a CO2 absorber, is subject to many restrictions in practical
with acetone to disperse K+ ions more evenly. At 400 ℃, application.
the absorption rate of CO2 was 22.9% higher than that of The active site of C O 2 absorption in MgO is
K-MG70. Subsequent work screened six impregnating sol- M g 2+-O 2− with low coordination. The coordination of
vents and demonstrated that ethanol dispersed K2CO3 doped O2− is primarily responsible for the interaction between
on the surface of LDH prepared using the AMOST method basic O2− and acidic CO2, and the oxygen atoms at the cor-
more efficiently than water (Zhu et al. 2020). ners and edges of the crystal surface are more alkaline than
those at the base surface. After absorbing carbon dioxide, a
MgO‑based absorbent single tooth matching body will be formed at the edge, and
a double tooth ligand will be formed at the corner.
In recent years, MgO-based absorbent has received more and The CO2-TPD curve indicates that the main factor affect-
more attention as a medium—temperature carbon dioxide ing the adsorption process, which can be classified into
absorber. MgO is abundant on Earth and has broad potential weak, medium, and strong types, is the number of basic sites
for CO2 capture due to its non-toxicity, low cost, relatively of MGO-based adsorbents. The required desorption temper-
low regeneration temperature and high theoretical adsorp- ature range was used to categorize each adsorption site, with
tion capacity. weak basic site < 473 K, medium basic site 473–573 K, and

tion of addition of K2CO3.
More low-coordinated sites
(edges and corners) are formed.
Supported LDH: LDH obtained
by deposition onto a carbon
nanofiber (CNF) support; light
gray spheres are magnesium;
red spheres are oxygen, and
dark gray spheres are potas-
sium. Reprinted with permis-
sion from Meis et al. (2010).
Chemical Society
strong basic site > 573 K. Additionally, as shown in Fig. 16, expected that the presence of S O2 will not significantly
the CO2 TPD profile reveals that bicarbonate, bicondentate reduce the cyclic carbon dioxide absorption capacity of MG-
carbonate, and monondentate carbonate are produced at, based adsorbents. However, magnesium-based adsorbents
respectively, weak, medium, and strong adsorption bases. require the promotion of molten alkali salts to quickly adsorb
Bicarbonate is produced when hydroxyl groups connect, CO2. How and to what extent the presence of S O2 affects
whereas bicondentate and monondentate carbonates are molten alkali salts and C O2 absorption capacity is unknown
produced when C O2 bonds with either M g2+ or O
2− (Cai and requires future work.
et al. 2015). In addition, the presence of H2O also affects the reac-
tion of magnesium with CO2, and in the carbonation pro-
Factors affecting CO2 capture cess, both the initial adsorbent (MgO) and Mg(OH)2 can
form MgCO3 in the presence of water. Figure 17 demon-
The main obstacles to the practical application of MgO strates that when the adsorption temperature is below the
adsorbent for C O2 capture lie in its poor adsorption kinet- transition temperature Ttr, the carbonation process takes
ics and low actual C O2 absorption rate, which are mainly Mg(OH) 2 + CO 2 ↔ M gCO 3 + H 2O as the main compo-
due to its poor alkaline active sites and high lattice enthalpy nent, while MgO carbonation occurs when the adsorption
(Hu et al. 2019). It is generally believed that the decrease temperature exceeds Ttr (Duan and Sorescu 2010). This is
of MgO absorption trend during high temperature exposure because at a transition temperature, MgO will react with
during CO2 capture is due to the decrease of SSA caused Mg(OH)2: MgO + H2O = Mg(OH)2, which is managed by
by sintering (Gao et al. 2018). Compared with the core, the pressure of water vapor. In the presence of water vapor and
low-coordination Mg2+-O2− sites at the corners/edges have at a lower system temperature, C O2 will be liberated from
better interaction with CO2. During the adsorption process, MgCO3 during the regeneration process and create Mg(OH)2
dense MgCO3 product layer will be formed, which encloses rather than MgO. In addition, when there is water present
the active MgO components in the core and hinders the dif- (approximately 10%), 80% of the conversion of MgO to
fusion and adsorption of C O2, resulting in inherently limited MgCO3 takes place at 623 K (Resasco et al. 2017). It has
adsorption performance. been postulated how MgO carbonizes when there is water
MgO will react with SO2 and O2 to form thermally stable vapor present. When MgO is surrounded by water, it forms
MgSO4 at a temperature much higher than the typical cal- CO32− and H ions. The free Mg2+ ion reacts with C O32− to
cination temperature of M gCO3. The formation of M gSO4 form MgCO3. This suggests that the chemisorption interac-
will reduce the amount of MgO in the adsorbent, so that tion between CO2 and MgO is improved by the role of water
the adsorption of CO2 is active. So far, the effect of S O2 vapor as a medium.
on the carbon dioxide absorption capacity of magnesium-
based adsorbents under relevant carbonation conditions Material optimization
has not been studied specifically. Early studies have shown
that the reaction of pure MgO with SO2 and O 2 is not obvi- Reducing particle size is an effective way to improve the
ous at 600 ℃. Recent studies have shown that MgO with CO 2 absorption capacity of metal oxides, because the
high surface area and porosity do react with SO2 and O2 reduction of particle size can expose more active sites of
at lower temperatures (~ 500 ℃) (Ani and Ebrahim 2021), metal oxides. Bian et al. (Bian et al. 2010) reported that
but sulfation of MgO at typical carbonation temperatures mesoporous MgO with high specific surface area and nar-
(~ 300–350 ℃) has not been reported. Therefore, it can be row pore size distribution was synthesized by thermal
Fig. 16 A schematic representation of the carbonate species formed on MgO-based adsorbents. Reprinted with permission from Ruhaimi et al.
(2021). Copyright 2021 Elsevier
at medium temperature. This explains why CS2Co3-doped

MgO has better CO2 absorption performance than pure
MgO. In addition, the CO2 absorption performance of MgO
can be improved by doping some metal oxides, such as TiO2,
Al2O3, ZrO2, etc.
In addition, MGO-based C O2 absorbers obtained from
the decomposition of double salt materials have high C O2
absorption capacity and special absorption characteris-
tics at medium temperature, which have been widely con-
cerned. In 2001, Mayorga et al. (2001) proposed for the first
time that double salts had great potential as an absorbent
of carbon dioxide at medium temperature. Their research
results showed that the absorptive capacity of double salts
of sodium and magnesium could reach 48.4 wt% at 375 ℃.
Zhang et al. (2013) proposed that the cycle absorption pro-
cess of C
O2 is carried out through the reversible reaction of
Fig. 17 Phase diagram for the MgO–(MgOH)2–MgCO3 system vs the Na-Mg double salt, which is as follows:
O2 pressure at fixed P
C H2O = 0.01, 0.1, 1.0, and 10.0 bar. Reprinted
with permission from Duan and Sorescu (2010). Copyright 2010 AIP
MgO + Na2 CO3 + CO2 ⇌ Na2 Mg(CO3 )2
Publishing
They mixed Na 2CO 3 and NaNO 3 with MgO to pre-
pare an absorbent with a high C O2 absorption capacity of
decomposition method. Compared with commercial MgO 3.4 mmol g−1(15 wt%). Lee et al. (2014b) reported that
nanoparticles, its CO2 absorption performance was greatly Na-Mg double salt was a special absorbent material. Experi-
improved. Ruminski et al. (2011) demonstrated that the CO2 ments confirmed that Na-Mg double salt had a very high
absorption performance of MgO is highly correlated with its absorptive capacity of 3.48 mol/kg (15.3 wt%) at 375 ℃, and
specific surface area. the absorbent had a good absorption/desorption kinetics, and
In general, the synergistic effect of the absorption site and could be easily regenerated by changing the temperature. Ji
the porous carrier is critical for the absorption of gas mol- et al. (2017) studied the synthesis of Na-Mg double salt and
ecules from the airflow, so a large number of studies have its performance for H2/CO2 separation. The CO2 absorption
emerged on the dispersion of MgO on the porous carrier. Liu capacity of the sample obtained under optimal conditions
et al. (2013b) loaded MgO nanoparticles (MgO NPs) onto was 17.9 wt% at 0.62 MPa and 375 ℃. Xiao et al. (2011a)
mesoporous carbon (MSC-MGO) to perform rapid pyroly- reported the MgO-K2CO3 absorbent applicable to PSA and
sis of MgCl2 waste biomass. The obtained sample MSC- TSA, during which double salt K 2Mg(CO3)2 was formed. In
MGO has excellent carbon dioxide capture performance, 100% CO2 atmosphere, the absorption capacity of 375 ℃ for
the maximum absorption capacity is 5.45 mmol g−1, and 2 h could reach 8.69 wt% (mass fraction). After 9 cycles of
has good cycling stability. After 19 cycles, the absorption dynamic absorption, the absorption capacity was basically
performance is almost unchanged, and can be regenerated at maintained at 7.5 wt % (conditions: 375–400 ℃, 100% C O2
low temperature. Kim et al. (2014) prepared core–shell MgO absorption for 20 min, N2 desorption for 30 min).
NPs@C nanospheres, and the 3 nm MgO NPs was directly By changing the pressure, setting a fixed temperature and
embedded into the carbon shell. The obtained absorbers evaluating the absorbent’s ability to absorb carbon dioxide
had high selectivity for C O2/N2, high absorption capacity within a certain period of time, Mayorga et al. (2001) reported
(5.3 mmol g−1) and good cycling stability. that the Na/K double salt ( Na2Mg(CO3)2/K2Mg(CO3)2) pre-
Alkali metal-modified MgO has received more and more pared by them kept the absorption temperature at 375 ℃ dur-
attention, and MgO loaded with potassium carbonate has ing the PSA process. The amount of carbon dioxide absorbed
good cyclic stability at higher temperatures. The absorp- by the absorbent can vary from 4.8 wt % to 57 wt %, mainly
tion capacity of K 2Co3-modified MgCO3 synthesized by due to the preparation method and the composition of the
Chaffe et al. (2007) was 1.8 mmol g−1 at 375 ℃ and 1 bar. final solid. When the partial pressure of C O2 is 10 atm, the
The maximum CO2 absorption capacity of C S2Co3-doped amount of CO2 absorption of the absorber can reach 75% of
MgO synthesized by Liu et al. (2013a) was 1.9 mmol g−1 the theoretical value. Singh et al. (2009) prepared Mg double
at 300 ℃. The experimental results showed that after CO2 salt, especially MG-Na double salt. When the temperature was
absorption, chemical reactions would occur to form Mg-Cs maintained at 375 ℃ in the PSA process, the maximum carbon
carbonate phase, and the activation energy of this reaction dioxide absorption can reach 20.68 wt%. Zhang et al. (2013;
was lower than that of the reaction between C O2 and MgO
2014) studied MGO-Na2CO3 absorbent, in which CO2 was and Favergeon 2013). It should be noted that only calcite is
absorbed by Na2CO3 and MgO in the form of Na2Mg(CO3)2, thermodynamically stable under typical carbonation condi-
and the absorption capacity was basically maintained at tions, although it also has the lowest adsorption preference
15.43 wt % after 10 cycles of dynamic absorption by temper- for CO2 of the three CaCO3 polymorphs (Zhang et al. 2020).
ature change (conditions: 380–470 ℃, 100% C O2 absorption Exothermic crystallization and the formation of amorphous
60 min, 100% CO2 desorption 10 min). CaCO3 are both possible at 300 ℃. Since the first surface
reaction happens quickly, exact control of the reaction condi-
tions is necessary for measuring intrinsic kinetics (Alonso
High temperature CO2 absorbent et al. 2014). The acceleration of carbonation implies the
hardly seen production and expansion of atomic nuclei
CaO‑based absorbent (Rouchon et al. 2014; Fedunik-Hofman et al. 2019) When
(PCO2—PCO2,eq) > 0.1 bar, the intrinsic rate constant for
Since 1933, numerous studies have been conducted on CaO- the CaO-CO2 reaction is shown to be zero-order depend-
based materials as high temperature carbon dioxide adsor- ent, but changes to be first order with respect to PCO2 (Sun
bents. Calcium oxide has high theoretical adsorption capacity et al. 2008). The activation energy of carbonation has been
and availability, showing great potential in C
O2 capture. After reported to be very low, usually less than 30 kJ mol−1 (Bia-
decades of research, more and more high performance calcium sin et al. 2015; Ramezani et al. 2017; Li et al. 2020). Shrink-
based carbon dioxide adsorbents have been reported, pushing age core, pore, and particle models, among others, have all
the research from basic to practical application. been demonstrated to be effective for kinetic modeling of
carbonation reactions (Chen et al. 2020a; Scaltsoyiannes
Absorption mechanism et al. 2021). The observed rate of carbonization declines,
as is common in many gas–solid interactions, until product
The cyclic adsorption–desorption of C O2 by CAo-based absor- layers of CaCO3 cover all available surface CaO.
bent is achieved by the chemical reaction of the CaO com-
ponent in the calcium-based absorbent with the CO2 in the Factors affecting CO2 capture
mixed gas to produce C aCO3, which is then calcined at high
temperature to release the C O2 and obtain the C
O2 with high In practical application, the desorption reaction of cal-
purity, which is convenient for storage or industrial applica- cium based absorbent is usually carried out at temperatures
tion. The CaO obtained after calcination can be recycled. This greater than 850 ℃, which can obtain high purity C O2 and
completes the process of cyclic adsorption–desorption of C O2 complete the regeneration of calcium based absorbent. How-
by calcium-based absorbent. The reaction principle is shown ever, it was later found that the absorption rate of calcium
in Eqs. (5.1) and (5.2). based absorbent decreased with the increase of the number
CaO(s) + CO2 (g) → CaCO3 (s) ΔH = −171.2kJ∕mol of cycles. There are three main reasons for the attenuation of
(5.1) CO2 absorption performance of calcium based absorbers: (1)
high temperature sintering; (2) product layer encapsulation;
CaCO3 (s) → CaO(s) + CO2 (g); (5.2) (3) the product layer obstructs micropores. Among them,
Since the carbonization reaction is exothermic, a signifi- the decrease of specific surface area and the closure of pore
cant amount of heat is generated that can be utilized in the structure caused by high temperature sintering are the main
carbon dioxide collection procedure. The decomposition of reasons for the decrease of absorbent activity.
carbonate (the calcination stage) is an endothermic reaction The sintering kinetics investigation reveals that lattice dif-
that is theoretically reversible and is more advantageous at fusion mostly governs the sintering of the CaO adsorbent.
higher temperatures. The reaction heat increases with the The surface free energy of the absorbent grains reduces as
molecular weight of the alkali earth metal oxides used as the calcination temperature rises to typically greater than
an adsorbent, but the energy density decreases. In the pro- 900 ℃, the grains fuse and grow, the grains in the aggregate
cess of cyclic adsorption and desorption of C O2 by calcium- continue to combine, and the giant grains engulf the small
based absorbers, many researchers have found that the initial grains and grow. Continuous aggregate shrinkage causes the
reaction of calcium-based absorbers in the process of C O2 volume of the entire calcium-based absorption particles to
absorption is a rapid reaction stage, which is controlled by decrease, specific surface area and porosity to decrease, and
kinetics. It is then controlled by slow diffusion. sintering to occur. In addition, the carbonization reaction
According to computational studies, calcite (CaCO3) transforms the outer CaO of the calcium-based absorber into
nucleates during carbonation on the surface of CaO with CaCO3, and the resulting CaCO3 product layer covers the
CO32− groups spreading laterally layer by layer (Besson unreacted absorber’s surface to stop further C O2 molecule
diffusion into the CaO particles. Furthermore, the particle
volume increases quickly during the adsorption process CO2 diffusion and O 2− migration are key factors in C
O2
because CaCO3 has a much larger molar volume (36.9 cm3/ capture. On this basis, Guo et al. (2017) reported a (Zr-Ce)
mol) than CaO (16.9 cm3/mol), which reduces the micro- additive that could promote the CO2 capture of grass-based
scopic void between particles, causes micropore blockage, adsorbents. Due to the formation of Ce2Zr2O7, oxygen
and raises the diffusion resistance of CO2. The capacity of vacancies are formed to facilitate the diffusion of C O2 and
CaO to absorb CO2 reduced. Accordingly, CaO-based CO2 O2− migration. Huang et al. (2017) created low melting point
adsorbent particles must not only be smaller in size and have eutectic doping of oxygen salts with CaO. By loading CaO
a higher specific surface area, but they must also maintain with alkali carbonate molten salt, its CO2 absorption during
a stable microstructure after repeated calcination, lower the the first carbonation was significantly increased from 3.26 to
regeneration temperature of calcination by altering the con- 10.94 mmol g−1 (Fig. 18a), which could be attributed to the
ditions, and lessen the sintering of CaO particles in order high O2− concentration and O2− conductivity of the molten
to maintain the high activity of CaO-based adsorbent after salt (Fig. 18b).
repeated capture. Florin and Harris (2008) discovered that the ability to
Limestone is introduced to the combustion zone of the cyclically absorb CO2 decreased after adding 1 wt% Li2CO3
boiler during high temperature flue gas desulfurization, to CaO. Similarly, Derevschikov et al. (2011) doped 8.6 wt
where it breaks down into CaO and CO2. CaO interacts % Li2CO3 into CaO and found that the C O2 absorption
exothermically with SO2 and O 2 during combustion to pro- capacity of doped CaO decayed faster than that of pure
duce CaSO4, which stops SO2 from being discharged into CaO. Nearly little Li was still present in the adsorbent after
the atmosphere (reaction 5.3). 18 trials with an isothermal thermogravimetric analyzer
of carbonization and calcination at 760 ℃. Salvador et al.
CaO + SO2 + 0.5O2 → CaSO4 ΔH850◦ C = −481.4kJ∕mol
(2003) noted that while some lime-doping combinations
(5.3)
had a beneficial impact in TGA trials (such as Havelock
If the smoke stream contains both C O2 and S O2, the two and Cadomin limestone doped with NaCl), doping natural
substances will compete for reaction with CaO (Chen et al. limestone with NaCl or N a2CO3 had a detrimental impact
2020b). At 600–700 ℃, the rate of sulphation is often faster on adsorption qualities in pilot fluidized bed combustor. In
than that of carbonation, although under the conditions of previous experiment, Manovic et al. found that sodium-rich
CaCO3 breakdown, the rate of reaction 5.3 increases with limestone (La Blanca) had poor cycling performance after
temperature and is thermodynamically viable (Manovic thermal pretreatment (Alvarez and Abanades 2005). In order
and Anthony 2010). When carbonization and sulfurization to explain this phenomenon, they mixed 5 wt % Na2CO3
take place at the same time, the diffusion resistance of C O2 into natural limestone (Kelly Rock) and studied the cycling
is increased because the molar volume of C aSO4 is larger performance (Manovic et al. 2008). Experiments showed
than CaCO3 (∼ 25%). The fact that CaO-based adsorbents that the presence of Na ions promoted the sintering of sam-
inactivated to CO2 are often more reactive to SO2 due to the ples, which was the main cause of deactivation. Xu et al.
optimal pore size being larger for sulphation than for carbon- (2018a) used NaBr as the dopant of CaO, and found that
ation is an intriguing result of the molar volume difference with the increase of the amount of NaBr (up to 10 mol %),
(He et al. 2016). Thus, during the charring-calcination cycle, the CO2 absorption capacity of 100 cycles increased. While
the adsorbent’s reactivity to S
O2 increases. The vulcanized NaOH and KOH did not considerably increase the absorp-
product CaSO4 is thermodynamically stable at typical calci- tion capacity of flowing CO2 and even sped up the deactiva-
nation conditions, which limits the effective C
O2 absorption tion of dopant adsorbents, NaCl and KCl were found to be
capacity in repeated cycles. This is another issue with SO2 efficient performance enhancers (Xu et al. 2018b). Seawater
in the flue gas. has been utilized to increase the cycling stability of CaO-
based adsorbents because it contains a variety of dissolved
Material optimization Na and K salts. The majority of research have found that
the accelerated sintering caused by saltwater doping reduces
Alkali metal doping In one of the first comprehensive the ability of circulating CO2 to be absorbed (Morona et al.
research on the influence of alkali metal promotion of CaO 2019; Chi et al. 2016). However, when only a little amount
sorbents for CO2, CaO was impregnated with up to 20 wt % of seawater was employed, an increase in C O2 adsorption
of Li, Na, K, Rb, or Cs using hydroxide and chloride precur- capacity was seen (Xu et al. 2016; González et al. 2020).
sors. At 600 ℃, the C O2 absorption was measured in pure
CO2. The absorption of CO2 is greatly enhanced by the dop- Inert stabilizers Theoretically, any form of metal oxide can
ing of Cs while it is adversely affected by the doping of other be used to stabilize the cycling characteristics of CaO-based
alkali metals. The properties of adsorbents improve with adsorbents as long as it has a melting point higher than that
increasing electropositivity/atomic radius of alkali metals. of CaCO3, has a low solubility in CaO, and (ideally) does
The creation of stable adsorbents by wet chemical processes

(such as sol–gel or coprecipitation) results in higher cycle
stability since these procedures have a higher degree of dis-
persion than mechanical mixing or impregnation (Huang
et al. 2018). In typical sol–gel procedures, metal alcohol
oxides are hydrolyzed and polymerized to create gels, which
are then dried and calcined to form (porous) solid metal
oxide adsorbent dry gels (Erans et al. 2016; Broda et al.
2012).
The sol–gel technique requires numerous reaction steps
and, in some circumstances, multiple reactors, making it
challenging to scale up for industrial applications. Broda
et al. (2014) created a more scalable “one-pot” recrystal-
lization technique where a CaO adsorbent stabilized at the
nanoscale was prepared using high Tammann temperature
MgO. In order to achieve high dispersion of inert support,
the precursors of calcium acetate and magnesium acetate
were recrystallized in organic solvents such as methanol,
ethanol, hexane, toluene and amyl alcohol under reflux con-
ditions. Organic solvents have a significant impact on the
surface area of crystalline calcium acetate, which varies
from 3 to 49 m2 g−1 in toluene and amyl alcohol, respec-
tively. In comparison, recrystallized magnesium acetate
had a surface area of 323 m2 g−1 with amyl alcohol. The
Fig. 18 a CO2 sorption/desorption cycling performance of CaO and adsorbent with a Ca/Mg molar ratio of 90/10 exhibited the
molten salt-promoted CaO. Reprinted with permission from Huang best absorption rate and crystallized again in amyl alcohol
et al. (2017). Copyright 2017 Wiley. b schematic diagrams of the among the materials under study. This ratio is assumed to
reaction with CO2 for low melting point oxy-salt eutectic coated CaO
particle. Reprinted with permission from. Copyright 2017 Royal represent a compromise between reduced active CaO for
Society of Chemistry CO2 collection and increased surface area and pore capacity
(high magnesium acetate concentration). Huang et al. (2018)
proposed a different innovative approach that just requires a
not interact chemically with CaO. As a result, with variable few reaction steps. In this approach, CaO-MgO composites
degrees of success, the oxides of other elements, includ- were made by combining the precursors of calcium acetate
ing Mg, Y, La, Ce, Pr, Yb, and Nd, have been researched and magnesium nitrate with water. Under constant agita-
as potential stabilizers of CaO (Hu et al. 2016; Daud et al. tion, non-solvent (ethanol) is added once it has dissolved.
2016; Yan et al. 2020; Nityashree et al. 2020). For instance, The stable chemical (i.e., magnesium nitrate) is soluble
it was discovered that La2O3 was (to a certain extent) active in both solvent and non-solvent, allowing it to distribute
in the adsorption of C O2 while stabilizing CaO (Orera well in solution. Ethanol lowers the solubility of calcium
et al. 2013). Metal oxides (such CeO2) have been found to acetate. In this approach, it is claimed that the non-solvent
increase CO2 movement within the adsorbent, boosting the drives phase separation during gelation at both the micro
rate of carbonization in addition to their structural stability and nano scales, which results in the production of the CaO
(Guo et al. 2018a). microstructure and MgO nanostructure that have been seen
From a purely geometric point of view, assuming equal (Huang et al. 2018). Following the formation of MgO nano-
particle sizes, 80% of the adsorbent particles should be sta- particles (50–100 nm) scattered on the surface of CaO as a
bilizers and 20% should be CaO, preventing direct contact stable CaO-based adsorbent, the resultant gel is calcined.
between CaO. In order to avoid a significant reduction in The use of organic precursors bears significant expenses for
the theoretical maximum C O2 absorption capacity, stabiliz- material synthesis, as Chen et al. (2020a) have noted, despite
ers are typically used in much lesser amounts in practice the fact that synthetic adsorbents made by wet chemistry
(typically ~ 10–25 wt%). As a result, there is always some produce materials with excellent C O2 capture capability in
degree of interaction between individual CaO particles and numerous cycles.
sintering. The support must be properly distributed among
the particles in order to serve as a physical barrier between Nano‑ and microstructured morphologies Some sci-
the CaO particles and avoid sintering following calcination. entists have achieved very porous adsorbents with
structural stabilizers by effectively utilizing template- a polycrystalline crystal film containing C aCO3, which was
assisted approaches to increase cycle stability. These inves- then processed again to create a hollow, sphere-shaped
tigations’ main objective is to create nano- and microporous nano- and micro-structured CaO-based crystal film.
structured adsorbents with less sintering during repeated Making core–shell structures is another method for reduc-
carbonation-calcination cycles. Figure 19 provides a sum- ing sintering deactivation. Here, highly porous adsorbents
mary of the various morphological stabilizing techniques. are likewise produced using template assisted technology,
The left and right columns, respectively, show the carbona- but instead of the stabilizer being distributed evenly, the
tion and calcination states. active absorber material is covered with a thin coating of
Nanostructured adsorbents with evenly dispersed stabi- the stabilizer. The goal of this specific form is to maintain a
lizers are created using sacrificed templates. Microtubules, high capacity with a limited amount of inert material. Sinter-
microspheres, nanosheets, and cage structures are some ing is hampered by the thin physical barrier, the shell, which
of the morphologies that occur. These structures are typi- restricts interaction between the calcium carbonate particles.
cally created using carbonaceous spheres as templates or Stabilizer layers can be added to the core adsorbent material
hard biomass templates like cotton, willow, straw, wheat, using vapor deposition techniques including atomic layer
and microalgae. However, there are some instances where deposition (ALD) and chemical vapor deposition (CVD).
hollow structures can be created using the Kirkendall effect The benefit of ALD technology is that it can produce a thin
without the use of a carbonaceous template (Zhang et al. conformal coating and control layer thickness at the atomic
2009; Huang et al. 2021). However, carbon templates are level. The method has been used to produce core–shell struc-
more typically utilized in the context of carbon dioxide captures for CO2 collection on porous CaO carriers with stabi-
ture. For instance, Broda et al. (2012) adopted a one-pot lizer oxide coatings ranging in thickness from 1 to 30 nm.
synthesis method in which aluminum and calcium nitrate It is important to note that the produced material forms a
precursors were mixed with gels. The carbonaceous sphere core–shell structure, but that throughout the multi-cycle
is covered with an amorphous calcium-aluminum-based procedure, it is also vulnerable to collapsing (Kim et al.
layer at the conclusion of the gel stage. Following a final 2019). Despite this collapse, compared to adsorbents with-
step of calcination in air at 800 ℃ to remove the carbon tem- out an ALD coating, the initial core–shell structure offers
plate, the gel was pyrolyzed in nitrogen at 500 ℃ to create considerably stronger carbon dioxide absorption stability.
Fig. 19 Schematic of nano- and

microstructured morphologies
to improve cyclic stability. The
left and right column shows the
carbonated and calcined states,
respectively. a Hierarchical
porosity obtained by template-
assisted techniques with a
homogeneous distribution of
the stabilizer or a stabilizer
coating providing a core–shell
morphology, respectively. b
Polymorphic and monomorphic
spacer used for a CaO sorbent.
Dunstan et al. (2021). Copy-
right 2021 American Chemical
Society
Although ALD treatment method can create adsorbents with theoretical absorption amount is about 28% (wt). Li2ZrO3
high activity and outstanding repeatability, Han et al. (Han can be prepared by mixing Li2CO3 and ZrO2 in different
et al. 2018) noted that its synthesis procedure is difficult and proportions, or LiOH can replace L i2CO3. The carbon
expensive. As an alternative, they advise employing chemi- absorption performance of L i2ZrO3 prepared by different
cal vapor deposition, which is more scalable and less expen- methods is also different (Duan 2011). Figure 20 shows the
sive. For this reason, assistive technologies like impregna- CO2 absorption process of L i2ZrO3, and the reaction equa-
tion, wet coating, or self-assembly templates are potential tion from inner layer to outer layer is as follows:
options that can offer great capacity at a lower price.
Inner layer ∶ Li2 ZrO3 → ZrO2 + O2− + 2Li+ (5.3)
Li2ZrO3/Li4SiO4 Outer layer ∶ CO2 + O2− + 2Li+ → Li2 CO3 (5.4)
A large number of comparative studies on lithium based At the beginning of the reaction, C O2 first diffused to
absorbers such as L iFeO 2, L iNiO 2, L i4TiO 4, L i 2ZrO 3, the surface of L i2ZrO3 particles and reacted with L i+ and
2−
Li4GeO4, Li4SiO4, LiSiO4, and L i2CuO2 have found that O to form ZrO2 and L i2CO3 cores. With the progress of the
although Li4TiO4 and Li4GeO4 can also absorb CO2 at high reaction, ZrO2 and Li2CO3 cores are gradually enlarged and
temperature. However, its absorption amount and absorp- connected together, forming a bishell structure with L i2CO3
tion rate were lower than Li2ZrO3 and L i4SiO4. Under high layer outside and Z rO2 layer in the middle on the surface of
i2ZrO3 and L
temperature conditions, L i4SiO4 have good high Li2ZrO3. After the formation of the double shell, the reac-
temperature carbon absorption performance, so many schol- tion rate began to decrease, because L i+ and O 2− had to
ars at home and abroad have paid attention to and studied pass through the Z rO2 shell to continue the reaction with
their structure and carbon absorption principle. CO2, and Z rO2 inhibited the diffusion of Li+ and O2−. Simi-
larly, the C
O2 molecule must pass through the L i2CO3 shell
to continue participating in the reaction. The Li2CO3 shell
Absorption mechanism
outside the ZrO2 shell inhibits the inward diffusion of CO2
molecules, and the C O2 absorption rate of L i2ZrO3 decreases
In 1998, Nakagawa and Ohashi (1998) of Toshiba Com-
under the action of the double shell. The diffusion rate of
pany in Japan reported for the first time that L
i2ZrO3 can
CO2 is the limiting step of this reaction process because
selectively absorb C
O2 in the range of 400–600 ℃, and its
the CO2 molecule is large and diffuses slowly. By raising

tion of the double-shell carbon-
ation-decarbonation mechanism
for Li2ZrO3. Reprinted with
permission from Buelens
et al. (2019). Copyright 2019
Elsevier
the temperature, the opposite desorption reaction can occur. between CO2 and lithium carbonate is the diffusion of C O 2,
The CO2 absorption of L i2ZrO3 also has some shortcom- and the doping of lithium silicate can form defects or reduce
ings, such as harsh synthesis conditions, low theoretical C O2 the melting point of the shell. At this time, the carbonate
absorption capacity, and strict atmosphere requirements. layer is in a molten state, which is conducive to the diffu-
Therefore, researchers need to do further research to over- sion of CO2, so the adsorption rate of lithium silicate can
come these shortcomings. be improved.
Lithium silicate is one of the best carbon absorbing mate- At present, lithium-based high temperature carbon
rials in the field of CO2 capture. In 2002, Kato et al. found absorbing materials can be prepared by solid-phase syn-
that the theoretical absorption value of lithium norosilicate thesis, sol–gel method, hydrothermal method, precipita-
could reach 36.7 wt% (Kato et al. 2002). Because of its fast tion method, citric acid ethanol complex method. Each
absorption rate and good cycle stability, it has become a preparation method has its own advantages and disadvan-
new high temperature carbon absorbing material with more tages: although the solid-phase method is simple, it has
application prospects than Li2ZrO3. At present, the adsorp- high energy consumption and low purity of the synthesized
tion process of carbon dioxide by lithium silicate is often product. Although the non-solid phase method can synthe-
explained by the bivalve mechanism (Kim et al. 2016a), as size relatively pure lithium-based high temperature carbon
shown in Fig. 21. The mechanism indicates that at the begin- absorbing material, its raw material cost is high.
ning of the reaction, carbon dioxide molecules are adsorbed
by the surface molecules of lithium silicate, and lithium pol- Material optimization
ysilicate and lithium carbonate are formed. As the reaction
goes on, lithium carbonate is coated with lithium polysili- For lithium-based carbon absorbing materials, no matter
cate, and lithium polysilicate is coated with lithium silicate, pure Li2ZrO3 or Li4SiO4, there is room for further improve-
thus forming a double-shell structure. Later, the internal ment of their CO2 absorption performance. The crystal struc-
lithium silicate reacts to form Li+ and O2−. The resulting ture can be improved by doping modification, and materials
ions are diffused to the surface of lithium polysilicate, while with different crystal types can be obtained to improve their
carbon dioxide passes through the lithium carbonate layer reaction speed or absorption capacity. The doping of metal
to react with the Li+ and O2− accumulated on the surface of ions makes Li compete with doped metal elements, resulting
lithium polysilicate. The equation of adsorption reaction is in structural changes of pure L
i2ZrO3 and L
i4SiO4 materials,
as follows: thus forming structural defects, as shown in Fig. 22. The
formation of this defect helps to improve the activity of the
Inner layer ∶ Li4 SiO4 ⇌ Li2 SiO3 + O2− + 2Li+ (5.5)
material, so that carbon absorption reaction is easy to occur.
For different metal elements, the optimal doping amount is
Outer layer ∶ CO2 + O2− + 2Li+ ⇌ Li2 CO3 (5.5) different, and the influence on the absorption stability of
lithium based high temperature carbon absorbing materials
Desorption occurs in the opposite way. This mechanism
is different. Metal elements such as K, Na, Fe, and Al are
can be used to explain why element doping can improve
usually used as doping elements.
the adsorption rate. The restricting factor of the reaction
Fig. 21 Double shell model

for CO2 sorption over L
i4SiO4.
Gao et al. (2020). Copyright
2020 Royal Society of Chem-
istry
Seggiani et al. (2011) modified Li4SiO4 with different and organic components typically become volatile and start
alkali metal carbonate (K2CO3, Na2CO3), two mixed carbon- to form pores. The thermally stable porous substance, on the
ate (K2CO3/Li2CO3, Na2CO3/Li2CO3) and three carbonate other hand, stays inside the sample, creating a second porous
(K2CO3/Na2CO3/Li2CO3). It is found that the addition of network. Not only does the existence of pores improve the
alkali metal carbonate can effectively accelerate the absorp- mass transfer phenomena, but it also expands the reactants’
tion rate and C O2 absorption capacity of the absorbent. It surface area in contact. L i4SiO4 adsorbents, for instance,
is worth noting that the addition of Na2CO3 will cause the have been created using polyethylene, porous carbon, and
sintering of the absorbent in the process of repeated use. For titanium dioxide nanotubes (Fig. 23).
the salt with high Li content (Li8SiO6, Li4SiO4, Li6Si2O7), Vermiculite is a natural mineral with a higher silicon con-
when the absorption temperature is lower than the conver- tent than fly ash (about 40%) and also contains various alka-
sion temperature of Li2SiO3, more C O2 can be absorbed to line earth metals and alkali metals (Mg, Al, K, etc.). Under
form Li2CO3 and S iO2. When the absorption temperature different operating conditions, the vermiculite synthesized
is higher than the conversion temperature of Li2SiO3, more Li4SiO4 has a higher adsorption capacity (20.7 wt %) and
CO2 can be absorbed to form L i2CO3 and SiO2. The absorp- good adsorption stability. Zhang et al. (2019) connected ver-
tion capacity of CO2 is low, and some L i2SiO3 still exists. miculite with MCM-41 mesoporous silica by hydrothermal
For salts with high Si content (Li2Si2O5, Li2Si3O7), from method to synthesize a new nanoparticle/flake composite
a thermodynamic point of view, they can absorb a small silicon source that could adjust the silicon content. The pre-
amount of carbon dioxide at a lower temperature. If the tem- pared Li4SiO4 has a high SSA (6.8 m2 g−1) and a high degree
perature is too low, the kinetics of the carbon dioxide capture of crystallinity, and the alkali or alkaline earth metals are
reaction will be too slow. evenly dispersed from the vermiculite. These characteristics
Xiao et al. (2011b) synthesized K-doped L i2ZrO3 absor- can improve the adsorption performance of Li4SiO4. Com-
bent with citrate, which has excellent CO2 absorption per- pared with the L i4SiO4 adsorbent obtained from a single sili-
formance. When the partial pressure of CO2 is 0.25 bar con source, (MCM-41/vermiculite)-Li4SiO4 exhibited higher
and K: Li: Zr is 0.2:1.6:1 at 550 ℃, the C O2 absorption CO2 adsorption capacity at low C O2 concentration and low
capacity of K-doped L i 2ZrO 3 can reach 5.2 mmol g −1 temperature, reaching 26.1 wt % at 550 ℃ and 20 vol% CO2.
within 15 min. Duan (2013) studied the structure, electron After 20 cycles, the adsorption capacity decreased about
and phonon properties of Li8ZrO6 using density functional 1.4 wt %. Generally, for the fabrication of efficient Li4SiO4
theory and lattice dynamics. The results show that the adsorbents by silicon precursor systems, it is required (but
lower the ratio of Li2O to ZrO2, the lower the conversion may not be sufficient) that they have a suitably high S iO2
temperature of L i2ZrO3. Therefore, by mixing or doping content, moderate levels of heat-stable impurities, and basic
two or more materials to form a new composite material, or alkaline chemicals.
it is possible to find or synthesize a high temperature CO2
absorbent that can meet the needs of industry with the best
performance. Summary and outlook
Another method to raise the effectiveness of an adsor-
bent is to include a pore-forming agent. Carbon materials, In this paper, the systematic process and characteristics of
organic compounds, or porous materials with good thermal each CO2 capture method are systematically introduced, the
stability at high temperatures are frequently used as pore- relevant research of each C O2 absorbent is reviewed, and
forming agents. At higher synthesis temperatures, carbon the advantages and disadvantages of each absorbent and the
Fig. 22 Schematic diagram of

the mechanism (replacement of
Li by foreign ions). Reprinted
with permission from Liu
et al. (2019b). Copyright 2019
Elsevier
Fig. 23 Li4SiO4 modification

by adding TiO2 nanotubes
and porous carbon. Reprinted
with permission from Lee and
Yavuz (2017). Copyright 2017
Elsevier
popular research directions are analyzed and compared. The factors affecting the practical application of this technology.
following is a summary of the important characteristics and The research direction is mainly to study the influence of the
cutting-edge technologies of each C O2 absorbent described preparation process of absorbent on the performance of absor-
in this paper: bent, investigate the factors affecting the carbonation reaction
rate of absorbent, and study the optimal conditions of carbona-
1. Liquid amine absorbent has a good effect on CO 2 tion reaction, such as reaction temperature, concentration of
absorption. It has the characteristics of fast CO2 absorp- water vapor and CO2 gas, airflow speed, etc. The cyclic reac-
tion rate, large amount of absorption, low cost, and can tion characteristics of solid absorbent were further studied, the
be recycled and recovered to high purity C O2. It is the absorption reaction process was studied from the perspective
most mature and widely utilized CO2 absorbent in the of absorption kinetics, and the reasons for the attenuation of
industry at present, although it has drawbacks like huge absorbent performance after carbonation reaction were found
energy consumption and equipment corrosion. The out, and certain measures were taken to improve and enhance
exploration of novel and efficient absorbers and the the carbonation reaction performance of absorbent.
development of CO2 capture processes with appropriate The adsorption capacity and selectivity of zeolite molecu-
thermal integration remain the main challenges for liq- lar sieve are good, but its regeneration ability is poor, and
uid amine CO2 capture. Promising amine solvents cur- the selectivity of CO2 separation of zeolite molecular sieve
rently under investigation include mixed amine solvents, from other gases ( H2O, CH4, N2, etc.) is relatively low, when
non-aqueous amine solvents, biphasic solvents and solid the temperature rises above 30 ℃, the absorption capacity
amine absorbers. Among them, the mixed amine sol- will be greatly reduced. The absorption capacity of zeolite
vent maintains the good carbon dioxide absorption per- molecular sieve basically disappears at temperatures above
formance, the absorption rate is fast, the regeneration 200 ℃. Additionally, the ability of zeolite-based materials
heat is low, can practically be utilized directly in the to absorb CO2 is greatly affected by the presence of water.
conventional amine absorption procedure. The viability It is a practical way to improve the gas separation perfor-
of using mixed amine solvents in place of conventional mance of zeolite by fine-tuning the internal pores of zeolite
monoamine has been confirmed by studies at both the and enhancing its adsorption characteristics. At the same
laboratory scale and in pilot plants, which has a promis- time, the additional type of skeleton cation has an impor-
ing industrial application prospect in the near future. tant effect on the C O2 capture capacity and pore volume of
zeolite. Zeolite adsorbents that are scalable and effective
At present, the main problems in the preparation process of can be created using the pore limitation method and used for
alkali metal carbonate absorbent are the selection of absorbent size-selective separation. In their industrial uses, zeolites’
carrier and the preparation process of absorbent. The carrier trade-off between adsorption capacity, diffusion dynamics,
materials with high specific surface area, high voids, high and mechanical stability still poses significant difficulties.
absorbability and wear resistance are suitable for the absor- MOFs have the advantages of abundant pore size, high
bent carrier, and the cost and source of materials are also adsorption capacity and large specific surface area, but the
majority of MOFs are unstable in hot, humid, and other hos- MgO has abundant reserves, low cost, non-toxicity, rela-
tile situations, making it challenging to achieve the demand- tively low regeneration temperature and high theoretical
ing industrial standards. For practical applications, the ther- adsorption capacity. The main obstacles to its application
mal stability of MOFs, particularly with respect to moisture in CO2 capture lie in its low actual C O2 absorption rate and
is crucial. The development of functional MOFs with high poor adsorption kinetics. In addition, the presence of H2O
mechanical and thermal stability is of great significance and also affects the reaction of magnesium with CO2. In order to
has been paid attention to and studied deeply. The introduc- enhance MgO’s capacity to absorb CO2 and cycling stabil-
tion of a strong nucleophilic Zn-OH group can enhance the ity of the adsorbent in the medium temperature range, many
CO2 absorption of MOFs at low pressure. Functionalized modification attempts have been made. The main measures
mesoporous polymer carriers play a key role in effectively include (1) reducing the size of MgO to synthesize porous
regulating the crystal growth of MOFs on local surfaces, MgO, (2) loading MgO nanoparticles on porous carrier, (3)
and the enhanced close interaction results in synergistic modifying MgO with alkaline carbonate, and (4) preparing
properties. The embedding of unsaturated alkali metal ions MGo-based mixed oxides.
into MOFs is another relatively direct method to improve Calcium based absorbent materials have good reaction
its CO2 affinity and corresponding adsorption properties. performance with CO2, and have the advantages of high
The performance of CO2 capture can be increased by adding absorption capacity, low material loss and low raw material
functional groups (tertiary amides or amines) to modify the cost. Low reversibility of the carbonation reaction brought
water adsorption capabilities that already exist in MOFs. on by the sintering of absorbent particles is the primary
Carbon-based materials have the advantages of cheap raw issue with CaO-based materials. Therefore, plenty of stud-
materials, easy regeneration, high porosity, high plasticity ies is focused on improving the sintering resistance of CaO-
of surface functional groups, and large specific surface area. based materials. Although the synthesis of CaO has made
However, due to the physical adsorption of carbon material great progress with regard to CO2 adsorption capacity and
absorbers in the process of C O2 absorption, the absorption cycle stability, its application is still constrained by its high
temperature is low and sensitive to temperature, and the cost and unstable nature. Future research directions should
selection of absorption is poor. Furthermore, the hydropho- focus on the following aspects : (1) Technology for large-
bicity of most porous carbon materials is poor, and the gas scale preparation of solid waste/mineral to create CaO with
discharged in industry often contains a certain amount of increased adsorption stability and capacity, as well as tech-
water, so enhancing a material’s hydrophobicity is essen- nology for catalyst loading for adsorption-enhanced hydro-
tial. At present, there are three methods used to enhance gen production; (2) material regeneration and CO2 separa-
the capture performance of carbon-based absorbent, includ- tion/purification technology; (3) direct utilization/conversion
ing adjusting the carbon's structural properties, chemically of CO2 fixed by calcium oxide adsorbent.
altering the carbon surface and creating carbon-based hybrid Lithium-based CO 2 absorbent not only has the theo-
composites. Enhancing the adsorbent-adsorbent interaction retical CO2 absorption value, but also has the character-
energy and improving the selectivity of CO2 absorption are istics of fast absorption rate and good cycle stability. Its
the main research directions. main disadvantage is that the reaction is limited by kinet-
Poor CO2 absorption capacity is the problem of LDH- ics. For lithium-based carbon absorbing materials, both
based CO2 absorbent. Although alkali metal doping can pure Li2ZrO3 and L i4SiO4 have room to further improve
enhance the C O2 capture capacity of LDH-derived CO2 their CO2 absorption performance. There are four ways to
absorbent, poor cycling stability and relatively low adsorp- improve the C O2 capture performance of lithium-based
tion capacity remain challenges. There are many researches absorbent: (1) Reasonable selection of raw materials and
on improving the C O2 capture performance and stability of preparation methods; (2) more pores can be formed by
LDH based absorbents. For example, research on Mg-Al- adding pore forming agent; (3) surface modification of
CO3 LDH mainly focuses on synthesis conditions, effects Li4SiO4 with molten salt; and (4) using silica-containing
of SOx and H2O, operating pressure, alkali metal doping minerals as precursors, impurity phase is used to improve
(K,Cs), particle size, and LDH loading on other carriers, stability and prevent sintering.
etc. Later research work focused on replacing C O32− ion or Through this review, we hope to help the academic cir-
2+ 3+
Mg and Al in Mg-Al-CO3 LDH with other anions or cle and industry to understand the latest progress in the
cations. In recent years, the research work on LDH-based research of various absorbent catalysts, build a bridge of
CO2 absorbent mainly focuses on the following areas: (1) communication between the absorbent under development
the insertion of organic anions, (2) the management of LDH and the objective needs of real production and life, and
particle size, (3) the creation of hybrid materials based on provide ideas for the innovative development of absorbent
LDH, (4) the method of doping alkali metals (Na, K, Cs), with more application prospects and better comprehensive
and (5) the investigation of absorption mechanism. performance.
in the Netherlands in the 2020s. Front Energy Res 9. https://

doi.org/10.3389/fenrg.2021.644796
Author contributions Hongtao Dang: conceptualization, methodol- Al Araj H, Bahamon D, Reddy KSK, Vega LF, Karanikolos GN
ogy, writing—original draft preparation, reviewing, editing and pol- (2023) A systematic approach to understanding and optimiz-
ishing. Bin Guan: conceptualization, writing—reviewing, validation, ing the CO2 capture performance of triamine-functionalized
and supervision. Junyan Chen: writing—original draft preparation and mesoporous silica with amine blends molecular simulations. J
reviewing. Zeren Ma: writing—original draft preparation. Yujun Chen: Phys Chem C 127:7410–7424
writing—original draft preparation. Jinhe Zhang: writing—original Alcañiz-Monge J, Marco-Lozar JP, Lillo-Ródenas MA (2011) CO2
draft preparation. Zelong Guo: writing- original draft preparation. separation by carbon molecular sieve monoliths prepared from
Lei Chen: writing—original draft preparation. Jingqiu Hu: writing— nitrated coal tar pitch. Fuel Process Technol 92:915–919
original draft preparation. Chao Yi: writing—original draft prepara- Alesi WR, Kitchin JR (2012) Evaluation of a Primary Amine-
tion. Shunyu Yao: writing—original draft preparation. Zhen Huang: Functionalized Ion-Exchange Resin for CO2 Capture. Ind Eng
supervision. Chem Res 51:6907–6915
Alkhatib III, Pereira LMC, AlHajaj A, Vega LF (2020) Performance
Funding This work was Sponsored by the National Natural Sci- of non-aqueous amine hybrid solvents mixtures for CO2
ence Foundation of China (52076134, 51676127, 51436005, and capture: a study using a molecular-based model. J CO2 Util
51176118), the National Key Research and Development Plan 35:126–44
(2016YFC0205200, 2016YFC0208000, and 2017YFB0103501), Alonso M, Criado YA, Abanades JC, Grasa G (2014) Undesired effects
the High-tech Ship Research Projects “Key combustion technol- in the determination of CO2 carrying capacities of CaO during
ogy research for ammonia-fueled marine engines based on the Otto TG testing. Fuel 127:52–61
cycle”, the Oceanic Interdisciplinary Program of Shanghai Jiao Tong Alvarez D, Abanades JC (2005) Pore-size and shape effects on
University (SL2022MS006), Major Science and Technology Projects the recarbonation performance of calcium oxide submitted
Yunnan Province (202402AC080004), the Open Research Program of to repeated calcination/recarbonation cycles. Energy Fuels
State Key Laboratory of Engines (K2023-06), Yunnan Precious Met- 19:270–278
als Laboratory Science and Technology Project, the National Engi- Ani AB, Ebrahim HA (2021) Comprehensive kinetic study of sulfur
neering Laboratory for Mobile Source Emission Control Technology dioxide removal by magnesium oxide using TG. J Therm Anal
(NELMS2017A07), the National Natural Science Foundation of China Calorim 146:2587–2599
for Young Scientists (51306115), the Low Speed Marine Engine Pro- Ansaloni L, Salas-Gay J, Ligi S, Baschetti MG (2017) Nanocellulose-
ject (CDGC01-KT1203), and the Scientific Research Foundation for based membranes for CO2 capture. J Membr Sci 522:216–225
the Returned Overseas Chinese Scholars of State Education Ministry. Arstad B, Fjellvåg H, Kongshaug KO, Swang O, Blom R (2008) Amine
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Environmental Science and Pollution Research (2024) 31:33259–33302

Research on carbon dioxide capture materials used for carbon dioxide

Research background Excessive greenhouse gas emissions will trigger global

Fig. 1 Process flow and key

Physical absorption method

Table 1 CO2 removal efficiency, energy consumption, and cost of C

Absorption (MEA) 85 to 90 3.80 62.80 Yun et al. (2020)

The main criteria for selecting adsorbents include spe-

Membrane separation method

Membrane separation is a new physical separation method

According to the total reaction formula, the theoretical

Fig. 4 NMR spectra of the

Non‑aqueous amine solvents is possible for non-hydroamine solvents to minimize energy

Fig. 5 a 13C NMR spectra and

Fig. 6 A possible two-stage

reacts with DMCA to form carbamate and ­D MCAH +

Solid amine adsorbents

Regeneration reaction ∶ 2MHCO3 (s) → M2 CO3 (s) + CO2 (g) + H2 O(g)

Fig. 8 a Scheme of the N

have a larger proportion of readily hydrolyzed bond binding

Extra‑framework cations In zeolite molecular sieve, the

The gas affinity can be greatly improved by fixing unsatu-

Fig. 11 Optimized geometries

Fig. 12 Different methods to

Fig. 13 Schematic representa-

Fig. 14 Schematic structure

layers can be peeled into nanosheets using “top-down” Absorption mechanism

Fig. 15 Schematic representa-

at medium temperature. This explains why ­CS2Co3-doped

The creation of stable adsorbents by wet chemical processes

Fig. 19 Schematic of nano- and

Li2ZrO3/Li4SiO4 Outer layer ∶ CO2 + O2− + 2Li+ → Li2 CO3 (5.4)

Fig. 20 Schematic representa-

Fig. 21 Double shell model

Fig. 22 Schematic diagram of

Fig. 23 Li4SiO4 modification

in the Netherlands in the 2020s. Front Energy Res 9. https://​

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reacts with DMCA to form carbamate and D MCAH +

at medium temperature. This explains why CS2Co3-doped

in the Netherlands in the 2020s. Front Energy Res 9. https://