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CO2 Capture by Solid-Adsorbents and Their Applications: Current Status and

New Trends

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Cite this: Energy Environ. Sci., 2011, 4, 42
www.rsc.org/ees REVIEW
CO2 capture by solid adsorbents and their applications: current status and new
trends
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Qiang Wang, Jizhong Luo, Ziyi Zhong* and Armando Borgna

Received 5th May 2010, Accepted 30th July 2010
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

DOI: 10.1039/c0ee00064g

In the last few years there has been a rapid growth in governmental funding and research activities
worldwide for CO2 capture, storage and utilization (CSU), due to increasing awareness of the link
between CO2 accumulation in the atmosphere and global warming. Among the various technologies
and processes that have been developed and are emerging for CSU of CO2, solid CO2-adsorbents are
widely applied. In this review, these solid CO2-adsorbents are classified into three types according to
their sorption/desorption temperatures: low-, intermediate- and high-temperature adsorbents with
temperatures ranging from below 200  C, between 200–400  C and above 400  C, respectively. For each
type of solid CO2-adsorbent, the synthesis, interaction mechanism with CO2 and sorption performance,
potential applications and problems are reviewed. In the last section, several representative CO2-
sorption-enhanced catalytic reactions are discussed. It is expected that this review will not only
summarize the main research activities in this area, but also find possible links between fundamental
studies and industrial applications.

1. Introduction 1956 to 2005) has almost doubled compared to that for the
period from 1906 to 2005.2
CO2 is the major anthropogenic greenhouse gas (GHG) in the The CO2 emissions associated with human activities are
atmosphere. Its atmospheric concentration has increased to 384 mainly due to the burning of fossil fuels and various chemical
ppm in 2007 from its pre-industrial level of ca. 280 ppm, and is processes, e.g., ca. 44% of anthropogenic CO2 emissions come
expected to reach 550 ppm by 2050 even if CO2 emission is stable from coal-, oil- or natural gas-fired power plants.2 Unfortunately
for the next four decades.1 One of the environmental impacts of there will be no big change in the next few decades for the energy
atmospheric CO2 accumulation is global warming. Indeed, it is consuming spectrum; fossil fuels will still be the dominant source
evident that a linear warming trend over the last 50 years (from as other energy sources such as biomass-based fuels, solar energy
and nuclear energy, which are CO2-neutral or do not emit CO2,
still cannot replace fossil fuels on a large scale. Moreover, the
energy demand will increase further by 53% by 2030.2 Since an
Institute of Chemical and Engineering Sciences, Agency for Science,
Technology and Research in Singapore (A*STAR), 1 Pesek Road, immediate CO2-emission halt is impossible, in recent years
Jurong Island, Singapore 627833. E-mail: [email protected]. worldwide efforts have been devoted to developing new tech-
sg; Fax: +65-83166182; Tel: +65-67963809 nologies/processes for CO2 capture, storage (sequestration) and

Broader context
There is a growing awareness that anthropogenic CO2 emissions should be reduced as CO2 is a major greenhouse gas in the
atmosphere. In order to do that, there are various measures which we can adopt: (1) change part of our current life styles, e.g., by
using less fossil fuels and adapting to greener technologies/processes; (2) seek alternative energy and chemical resources; (3) capture,
store and utilize (CSU) part of the emitted CO2. For the 3rd option, solid CO2-adsorbents will play an important role. For any
practical application of these solid CO2-adsorbents, not only should we take into consideration their sorption capacities, selectivities
and recyclibilities, we should also look into other factors, e.g., their working temperatures, which should be compatible to that of the
particular process. In addition, in some reactions that produce CO2 as one of its products, CO2-removal is likely to influence the
outcome of the reactions. Thus, this will probably widen the application of these materials in catalysis. In light of the increasingly
obvious global warming trends worldwide, capture, storage and utilization of CO2 by means of solid CO2-adsorbents via a number
of environmentally friendly processes is of increasing importance. Meanwhile, it will create new business opportunities.

42 | Energy Environ. Sci., 2011, 4, 42–55 This journal is ª The Royal Society of Chemistry 2011
 View Online

utilization (CSU), and to improving the energy utilization effi- Unlike liquid adsorbents, solid adsorbents can be used over
ciency.3 Among them, sorption-based technologies and processes a wider temperature range from ambient temperature to 700  C,
account for the majority of these research activities, and they yield less waste during cycling, and the spent solid adsorbents can
usually involve solid CO2-adsorbents. For example, in order to be disposed of without undue environmental precautions.7
remove CO2 from power plant flue gas, which is crucial for large In the last few years there has been a rapid growth in publi-
scale CO2-emission reduction, three kinds of technologies have cations related to CSU of CO2, and several recent review
been developed and tested, including post combustion, pre- papers2,4,8 provide very good insights into the progress in this
combustion and oxyfuel.4 Some solid CO2-adsorbents have been area. However, we feel that a new review focusing on solid CO2-
tested in the post combustion and pre-combustion capture adsorbents, addressing their pros and cons, and potential
processes,5,6 though presently almost all commercial processes applications in industry is still needed. Furthermore, in this
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for capturing CO2 still use liquid alkaline solutions (e.g. amine). review, we will not only summarize the latest progress in the
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

Qiang Wang is a Research Ziyi Zhong received his BSc and

Fellow in the Institute of MSc degrees from Wuhan
Chemical and Engineering University and obtained his PhD
Sciences (ICES) under from Nanjing University in
A*STAR, Singapore. He China in 1995. He spent five
received his BSc (2003) and years carrying out postdoctoral
MSc (2005) from Harbin research at Bar-Ilan University,
Institute of Technology (HIT) the University of Washington
in China, and his PhD (2009) and finally at the National
from Pohang University of University of Singapore. In
Science and Technology 2002, he was awarded a Visiting
(POSTECH) in South Korea. Fellowship by NSERC Canada
His research interests are and worked in an institute
Qiang Wang heterogeneous catalysis and Ziyi Zhong (BRI) in Montreal. Since 2003,
materials chemistry, with he has been working in the
a particular focus on CO2 Institute of Chemical and Engi-
capture and utilization, hydrogen production, vehicle emission neering Sciences in Singapore, researching environmentally related
abatement, biomass conversion, and synthesis and applications of heterogeneous catalysis. So far he has published 90 journal papers,
porous materials and nanocomposites. He was awarded the a book chapter and filed two patents.
Chinese Government Award for Outstanding Self-Financed
Students Abroad in 2008.

Jizhong Luo obtained his PhD Armando Borgna (PhD in

from Xiamen University in 1997. Chem. Eng., Universidad
After two years of postdoctoral Nacional del Litoral, Argentina,
research at Hong Kong Baptist 1987) is a Senior Scientist and
University, he joined the Physics Programme Manager at ICES
Department of the National (A*STAR, Singapore). He is
University of Singapore as also an Adjunct Associate
a research fellow in 2000. In Professor at the Department of
2003, he joined the Institute of Chemical and Biomolecular
Chemical & Engineering Science Engineering, National Univer-
(ICES), and he is now a senior sity of Singapore. He was
research follow in the Applied previously a postdoctoral
Catalysis group. His research researcher at the Institut de
Jizhong Luo interests include heterogeneous Armando Borgna Recherches sur la Catalyse,
catalysis, alternative energy, CNRS (1987–1990),
microwave chemistry, and the Researcher at the Institute of
carbon credit market. Research on Catalysis and Petrochemistry, CONICET-Argentina
(1991–2001), and Senior Research Associate at TU-Eindhoven
(2001–2004). He was a Fulbright Fellow at the University of
Oklahoma (1999). His research interest is in heterogeneous
catalysis, particularly characterization of working catalysts,
kinetic modeling and mechanistic studies.

This journal is ª The Royal Society of Chemistry 2011 Energy Environ. Sci., 2011, 4, 42–55 | 43
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synthesis and applications of various solid CO2-adsorbents, but to be disposed of.29,31 All of the above mentioned research
also organize these materials into different types according to activities on carbon-based CO2-adsorbents are summarized in
their properties and performances, e.g., their working and Fig. 1.
regeneration temperatures, and associate them with various
application processes. In addition, we will also address repre-
sentative catalytic applications for the solid adsorbents, which is 2.2 Zeolite based adsorbents
an active research topic with plenty of room for further devel-
Zeolites are porous crystalline aluminosilicates, whose frame-
opment. This is based on the fact that since some catalytic
work consists of interlocking tetrahedrons of SiO4 and AlO4
reactions generate CO2 as one of the products, integration of
joined together in various regular arrangements through shared
a solid CO2-adsorbent with the catalyst is expected to shift the
oxygen atoms. They have open crystal lattices containing pores
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reaction balance. This will probably widen the application of

with molecular dimensions, into which molecules can penetrate.
solid CO2-adsorbents. However, some other topics such as the
The negative charge created by the substitution of an AlO4
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

storage of enriched CO2 in proper geologic formations, catalytic

tetrahedron for a SiO4 tetrahedron is balanced by exchangeable
conversion of CO2 to some value-added chemicals and utilization
cations (e.g., Na+, K+, Ca2+, Mg2+), which are located in the
of CO2 as a solvent in chemical reactions will not be included.
channels and cavities throughout the structure. The adsorption
and gas separation properties of zeolites are heavily dependent
on the size, charge density, and distribution of these cations in
2. Low-temperature solid adsorbents (< 200  C)
the porous structure.33 The CO2 adsorption mechanism on
2.1 Carbon based adsorbents zeolites has been investigated by various groups and it has been
revealed that the physisorption of CO2 occurs with CO2 in
Owing to their low cost, high surface area, high amenability to
a linear orientation by an ion–dipole interaction (reaction 1).34,35
pore structure modification and surface functionalization, and
relative ease of regeneration, carbon-based materials are (metal ion)x+ // d
O]C]Od+ (1)
considered to be one of the most promising adsorbents for
capturing CO2 in integrated gasification combined cycle (IGCC) In addition to physical adsorption, more strongly bound
processes for energy generation and hydrogen production.9 carbonate species are also observed. These adsorbed CO2 sites
However, the CO2 adsorption on carbon materials is ‘‘physical’’ are bent and associated with bi-coordination, as shown in
and weak, which makes these adsorbents sensitive to temperature Scheme 1.34,35
and relatively poor in selectivity. The CO2 sorption capacity Although zeolites have shown promising results for separating
drops dramatically at temperatures associated with power plant CO2 from gas mixtures and can potentially be used in the pres-
flue gas (50–120  C).10 Thus current research efforts are focused sure swing adsorption (PSA) process, their selectivity to CO2
on how to enhance the adsorbate–adsorbent interaction and the over other gases (N2, CH4, H2O, etc.) is still low, and their
selectivity for CO2. One approach is to increase the surface area adsorption capacities rapidly decline with increasing temperature
and tune the pore structure of the carbon adsorbents either by above 30  C and become negligible above 200  C.36–38 Generally
using different precursors,11 or forming different structures such
as single-walled carbon nanotubes (CNTs),12 multi-walled
CNTs,13–15 ordered mesoporous carbon,16 microporous carbon,17
etc. Another efficient approach is to increase the alkalinity by
surface modification. This can be achieved either by impregna-
tion of additives such as 3-chloropropylamine-hydrochloride
(3-CPAHCl)18 and polyethylene glycol (PEG),10 or by incorpo-
ration of basic nitrogen groups into the carbon framework.19–21
Arenillas et al.10 impregnated several organic bases on fly ash-
derived carbon materials, and observed a CO2 capture capacity
of 1.13 mmol g1 at 75  C. It should be noted that, although the
impregnation method is often used, the adsorbate–adsorbent
interaction is weak thus the recycling ability is not strong.
Moreover, the introduction of additives may block the porous
carbon structure, thus lowering the adsorption capacity.22,23
Nitrogen can be incorporated into carbon structures by
preparing carbon adsorbents from N-containing polymers, or by
heat treatment of carbon adsorbents with NH3,23,24 or amines.25–27
Recently Hao et al.28 synthesized a new nitrogen-doped porous
carbon monolith, for which a very high CO2 adsorption capacity
of 3.13 mmol g1 was achieved at room temperature and 1 atm. Fig. 1 A summary of current research activities on carbon-based CO2-
To decrease the cost of the adsorbents, cheaper carbon resources adsorbents. The middle part shows the types of carbons adsorbents that
such as fly ash,29 almond shell-derived carbon,30 or anthracite25 have been studied, the left part shows the impregnation or grafting of
can be selected. This is especially the case for the waste recycling basic additives, and the right part shows the incorporation of N-con-
of fly ash which cannot be marketed as a cement extender and has taining groups.13,22,24,26,32

44 | Energy Environ. Sci., 2011, 4, 42–55 This journal is ª The Royal Society of Chemistry 2011
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CaY- and NiY-zeolite is scanty in the presence of water, because

water is preferentially adsorbed onto these surfaces. Later Rege
et al.56 and Brandani et al.57 observed that H2O has a strong
effect on CO2 adsorption on type X zeolites. From a thermody-
namic viewpoint, the adsorption of CO2 in the presence of H2O is
not favored.58 However, Dıaz et al.42 found that the CO2
Scheme 1 Two types of carbonate species associated with bi-coordina-
adsorption on Cs- and Na-treated Y zeolites increased after
tion. water treatment, and believed that it was due to the enhancement
in the Brønsted acidity in zeolites after treatment with alkali. The
number of acid sites presumably increased after alkaline treat-
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speaking, separation of gases by zeolites depends on three ment (both with CsOH and NaOH), and the water molecules
factors: structure and composition of the framework, cationic could coordinate to the Lewis sites and create new Brønsted acid
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

form, and zeolite purity.39 A number of zeolites, especially those sites. In addition, H2O may have a detrimental effect on the
which are highly crystalline, with high surface area, and three- stability of zeolite frameworks. In the presence of CO2, the acidic
dimensional pore structures, have been investigated, including conditions may cause dealumination of the zeolite structures,
zeolite X,37,40,41 Y,42,43 A,44 b,45 ZSM,46,47 CHA,48 and natural leading to a partial or total destruction of the framework. Ertan
zeolites (e.g. ZAPS, ZNT, ZN-19).39 Harlick et al.49 studied 13 et al.59 studied CO2 adsorption on acid (HCl, HNO3, H2SO4,
types of zeolite-based adsorbents, and concluded that the most H3PO4) treated zeolites, and found that their CO2 adsorption
important adsorbent characteristics are a near linear CO2 capacities decreased after the acid treatment.
isotherm and a low SiO2/Al2O3 ratio with cations that have
a strong electrostatic interaction with CO2. Siriwardane et al.50
2.3 Metal organic framework based adsorbents
reported that the CO2 adsorption capacity for zeolites 13X and
4A were about 3.64 and 3.07 mmol g1 respectively at 25  C and 1 Metal organic frameworks (MOFs), which are constructed from
atm of CO2 partial pressure. Inui et al.36 studied the adsorption transition metal ions and bridging organic ligands, are a new
behavior of different zeolites in the PSA process and claimed that family of porous materials.60,61 One type of MOF structure
CHA and 13X were the most appropriate for CO2 separation (indium soc-MOF) is shown in Fig. 2, in which (a) is a cluster of
among the zeolites studied. Merel et al.44 investigated the CO2 metal ions (indium-carboxylate trimer, TMBB, In3O-
capture of zeolites 13X and 5A by indirect thermal swing (CO2)6(H3O)3), (b) is an organic linker (3,30 5,50 -azobenzenete-
adsorption, and found that zeolite 5A performed better than tracarboxylic acid), (c) and (d) are representations of a cuboidal
13X. Calleja et al.51 reported that the preference of the adsorbent cage of indium soc-MOF and (e) is a space filling representation
for polar molecules (e.g. CO2) increases as the Si/Al ratio of the framework viewed along the y-direction. The CO2
decreases due to the higher surface heterogeneity and the adsorption and desorption in MOFs, which are ascribed to
stronger electrostatic field inside the pores of the zeolite. changes in the framework structures, are explained by
Another research area is the zeolites exchanged with alkali and a ‘‘breathing-type mechanism’’ or a ‘‘gate effect mechanism’’.62–64
alkaline-earth cations. The cations influence the electric field Normally the interaction between adsorbed CO2 and adsorbents
inside the pores as well as the available pore volume, and provide is weak, and the species starts to desorb when the temperature is
a convenient means for tuning adsorptive properties of these higher than 30  C. It should be noted that the MOFs used for
porous materials. Walton et al.52 studied the CO2 adsorption CO2 capture are not limited to this type of structure.
behavior of the Y and X zeolites exchanged with Li, K, Na, Rb, Owing to their very high porosity and surface area, ordered
and Cs, and found that the largest CO2 capacity was obtained for and well characterized porous structure, and adjustable chemical
the zeolite containing Li. It was suggested that the CO2 molecule functionality, MOFs are attracting increasing attention in CO2
possesses a quadrupole moment that can interact more strongly capture.66 Millward et al.67 reported that, at 35 bar, a container
with smaller cations like Li. Dıaz et al.42 evaluated the Na- and filled with MOF-177 could capture nine times the amount of CO2
Cs-treated Y zeolites, and suggested that Cs–Y is a promising in the container (33.5 mmol g1) compared to that without the
material for CO2 adsorption processes at relatively high
temperatures. Yamazaki et al.53 and Wirawan et al.46,54 investi-
gated the CO2 adsorption on cation-exchanged MZSM-5 (M ¼
Li, Na, K, Rb, Cs, H, Ba) and observed that, compared to other
cation-exchanged zeolites, BaZSM-5 has a higher CO2 adsorp-
tion capacity and the adsorbed species also has a higher thermal
stability. Zhang et al.48 found that NaCHA and CaCHA have
comparative advantages for high temperature CO2 separation
whilst NaX shows superior performance at relatively low
temperatures.
In terms of practical applications, moisture is another chal-
lenge to zeolite based adsorbents. H2O is an important compo-
nent in boiler flue gas and some other industrial gases, and it may
compete with CO2 for the active adsorption sites. Gallei et al.55 Fig. 2 X-ray crystal structure of indium soc-MOF. Color scheme:
have reported that the physical adsorption of carbon dioxide on carbon ¼ gray, oxygen ¼ red, nitrogen ¼ blue, indium ¼ dark green.65

This journal is ª The Royal Society of Chemistry 2011 Energy Environ. Sci., 2011, 4, 42–55 | 45
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adsorbent. Llewellyn et al.68 obtained a record capacity of was subjected to a gas stream containing 20% CO2 in CH4,
40 mmol g1 for CO2 capture with MIL-101 at 50 bar and 30  C. a percentage in the range of industrial separation conditions, it
In order to be applicable to realistic flue streams, MOF-based captured only CO2 and not CH4. The porous material retained
CO2-adsorbents should fulfil the following requirements: high 89 g of CO2 per kilogram of material before breakthrough
CO2 capture capacity and selectivity for CO2 over other (2.23 mmol g1). Furthermore, these unsaturated metal sites can
components in the flue gas, corrosion resistance, and high be functionalized with groups such as amine to further improve
thermal/hydrothermal stability, etc. To date, although MOFs their performance.66,69,73–75 Demessence et al.66 functionalized the
have shown exceptionally high CO2-storage capacity under triazolate-bridged MOF 1 (Cu-BTTri) with ethylenediamine, and
equilibrium conditions with pure CO2, most of them show little obtained a very high uptake of CO2 at low pressures (see
uptake in the low pressure regime of 0.1–0.2 bar, which is the Fig. 3(b)). This material also displayed a record isosteric heat of
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pressure range used for CO2 capture from flue gas streams.66 90 kJ mol1. Bae et al.75 reported that the CO2/N2 selectivity
Even worse, their capacities reduce dramatically when exposed to could also be enhanced by a cavity modification. By replacing the
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

mixtures of gases under dynamic conditions, which would be the coordinated solvent molecules with highly polar ligands, a high
case in power plant flue gas and methane mining applications.69 CO2/N2 selectivity of 42 was obtained at low pressure. Couck
Therefore, tremendous efforts have been made to further et al.73 demonstrated that the MOF MIL-53(Al) functionalized
increase their CO2 capture selectivity while maintaining or with amino groups increased its selectivity of CO2/CH4 by orders
improving their capture capacity under equilibrium conditions. of magnitude while maintaining a very high capacity for CO2
The modifications are usually conducted in three aspects: (a) capture. In addition to amines, the occupation of open metal sites
metal ions, (b) organic linkers, or (c) novel combinations of both. by coordinated water molecules has also been studied
For the metal ions, creating open metal sites has been proven (Fig. 3(c)).76,77 Yazaydin et al.76 first predicted by molecular
to be an efficient approach, as the vacant coordination sites at simulations and then validated by experiments that water
metal ions are the primary coordination sites for guest mole- molecules coordinated to open metal sites could significantly
cules.69–72 Britt et al.69 reported that a MOF replete with open increase CO2 adsorption in Cu-BTC.
magnesium sites, Mg-MOF-74 (Mg2(DOT); DOT: 2,5-dioxido- For the modification of organic linkers, Bae et al.60,78 examined
terephthalate), has excellent selectivity, facile regeneration, and is the possibility of using MOFs that are carborane-based or
ranked among the highest dynamic capacities reported for CO2 coordinated with a mixture of ligands, and obtained a high
in porous materials (Fig. 3(a)). In particular, when Mg-MOF-74 selectivity for CO2 over CH4 (17).78 Carboranes possess several
favorable material properties including rigidity, thermal
stability, and chemical stability. In addition, carboranes can
produce MOFs with smaller pores than phenyl-based MOFs.
The use of two different linkers opens up more possibilities to
tune pore size and chemical functionality independently. The
mixed ligand MOF Zn2(NDC)2(DPNI), 2, (NDC ¼ 2,6-naph-
thalenedicarboxylate, DPNI ¼ N,N0 -di-(4-pyridyl)-1,4,5,8-
naphthalene tetracarboxydiimide) exhibited a selectivity of 30
for CO2 over CH4.78
Much attention has also been paid to the synthesis of novel
MOFs with both high CO2 capture capacity and stability. The
ability to synthesize MOFs with various organic linkers and
metal joints provides tremendous flexibility in equipping the
porous material with specific physical characteristics and chem-
ical functionalities. Recently, a big breakthrough has been made
by Yaghi’s research group in UCLA.79,80 A new class of MOFs
known as zeolitic imidazole frameworks (ZIFs), in which metal
atoms such as Zn are linked through N atoms by ditopic
imidazolate (C3N2H3 ¼ Im) or functionalized Im links to form
neutral frameworks. These compounds have high chemical and
Fig. 3 (a) Single crystal structure of Mg-MOF-74, formed by reaction of thermal stabilities (up to 500  C).81 Phan et al.82 reported that 1 L
the DOT linker with Mg(NO3)2$6H2O. C atoms are shown in gray, O of ZIF-69, the best-performing ZIF, could store 82.6 L of CO2 at
atoms in red, 6-coordinate Mg atoms and terminal ligands in pink, and 5- 0  C. In addition, ZIFs show greater selectivity than other types
coordinated Mg atoms in blue. H atoms and terminal ligands on the of MOFs for CO2 from relevant flue gases. It is believed that only
fragment in the top right are omitted for clarity.69 (b) A portion of the CO2 can slip into the cages within the ZIF, while other gas
structure of the sodalite-type framework of Cu-BTTri (1) showing surface
molecules just pass through them without hindrance.83 There-
functionalization of a coordinatively unsaturated Cu2+ site with ethyl-
fore, ZIFs are a very promising type of material for selective
enediamine, followed by attack of an amino group on CO2. Purple, green,
gray, and blue spheres represent Cu, Cl, C, and N atoms, respectively;
adsorption of CO2, and they are twice as efficient as BPL carbon
framework H atoms are omitted for clarity.66 (c) Hydrated Cu-BTC (4 wt (a commercially available carbon product of Calgon).84 Yaghi’s
%) with a coordinated water molecule from DFT. Cu atoms are orange, group have also developed another class of new porous crystals,
O red, C gray, and H white. The oxygen atom of the coordinated water covalent organic frameworks (COFs), by condensation reactions
molecule is shown in blue.76 of phenyl diboronic acid (C6H4[B(OH)2]2) and

46 | Energy Environ. Sci., 2011, 4, 42–55 This journal is ª The Royal Society of Chemistry 2011
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hexahydroxytriphenylene (C18H6(OH)6).85,86 Recent studies 2.5 Amine-based solid adsorbents

indicated that COFs also have a comparable capacity for CO2
Some NHx-containing organics or polymers can chemically bind
adsorption to the most common carbon materials, zeolites,
to acidic CO2 molecules at low reaction temperatures, and thus
mesoporous solids, MOFs, etc.87
they are potentially good candidates for CO2 capture. CO2
removal from flue gas by sorption and stripping with aqueous
amines (commonly monoethanolamine (MEA), diethanolamine
2.4 Alkali metal carbonate based adsorbents (DEA) and methyldiethanolamine (MDEA)) has been estab-
lished since 1930 and is still believed to be a feasible tech-
Thermodynamic analysis of dry and re-generable adsorbents has nology.102,103 However, this process suffers from a series of
shown that alkali metal carbonates are suitable for the treatment
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inherent problems, including the corrosive nature of the amines,

of flue gases at temperatures below 200  C.88,89 Typically CO2 high regeneration energy, fouling of the process equipment,
capture is effective within the temperature range of 50–100  C, etc.104,105 In order to avoid the above problems, intensive efforts
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

while regeneration occurs in the range of 120–200  C. This have been made to prepare amine-based solid adsorbents by
concept is potentially applicable to the capture of CO2 from immobilizing organic amines on certain support mate-
existing fossil fuel-fired power plants. rials.26,50,106–108 Compared to the aqueous amine solutions, the
Liang et al.90 studied the mechanism and revealed that the solid amine adsorbents usually require lower capital cost, lower
important reactions involved in the capture of CO2 using pressure for gas recovery, and lower energy consumption for
Na2CO3 are shown in reactions (2) and (3). regeneration.109 Research activities have been focused on three
aspects to improve the CO2-capture properties of amine-based
Na2CO3(s) + CO2(g) + H2O(g) 5 2NaHCO3(s), solid adsorbents: (1) supports that are able to bear high amine-
DHr ¼ 135 kJ mol1 Na2CO3 (2) loading, (2) amines that can generate high amine density, and (3)
effective methods for amine immobilization.
Na2CO3(s) + 0.6CO2(g) + 0.6H2O(g)
Generally speaking, the supports should have a good affinity
5 0.4[Na2CO3$3NaHCO3](s),
for the amine molecules, high surface area, proper porosity, good
DHr ¼ 82 kJ mol1 Na2CO3 (3)
mechanical strength and hydrothermal stability, etc. Silica,
carbon, polymers such as resin, glass and metal oxides can be
The theoretical CO2 capture capacity of Na2CO3, calculated
considered, but usually porous materials are preferred due to
from reactions (2) and (3), is 9.43 mmol g1 and 5.66 mmol g1
their high surface areas and large pore size and volume. In other
respectively. Both reactions are reversible and highly exothermic
words, nonporous and even microporous materials are rarely
so energy management is an issue that should be considered in
selected for the purpose. Among various porous candidates,
any particular application. K2CO3-based adsorbents have also
mesoporous silicas (SBA-15, MCM-41, etc.) are most widely
been investigated and showed similar results.91,92 The conversion
investigated, mainly because of the ‘‘silane chemistry’’; a number
decreases with an increase in the reaction temperature and
of aminosilanes can react with the silica surface via alkyl–silyl
pressure, and varying the CO2 and H2O concentrations has little
linkages, thus providing vast opportunities for loading amine
effect, while the maximum reaction rate increases with an
molecules onto the supports. Harlick et al.110 did systemic work
increase in temperature and H2O concentration, and with
on pore-expanded MCM-41 (PE-MCM-41) grafted with 3-[2-(2-
a decrease in pressure. The carbonation can start from 60  C, and
aminoethylamino)ethylamino]propyl trimethoxysilane (TRI),
the maximum carbonation temperature is limited by the reaction
and found that the TRI-PE-MCM-41 adsorbent showed a higher
thermodynamics.90 As a result, a common problem is that the
CO2-sorption capacity and kinetics than TRI-MCM-41. One of
overall carbonation reaction rate for Na2CO3/K2CO3 is rather
the drawbacks of these mesoporous silicas is their relatively weak
slow. Many attempts have been made to resolve this, e.g., by
hydrothermal stability, probably limiting their application in
dispersing active Na2CO3/K2CO3 on a support such as Al2O3,
aqueous media. Amination of carbon materials is also reported
active carbon (AC), TiO2, SiO2, MgO, ZrO2, etc., so as to
by reacting carbon surface carboxylic groups with halogenated
enhance the adsorption rate and provide the required attrition
amine molecules.26 This kind of material has been addressed in
resistance in the fluid-bed or transport reactors.7,90,93–98 Never-
section 2.1 and is probably better suited to aqueous media.
theless, these adsorbents have a disadvantage in that the reac-
Various amines tested for CO2 capture include alkanolamines,
tivity always decreases with increases in sorption/regeneration
mono-, di-, and triaminosilanes, aminopolymers such as poly-
operations.99,100 Okunev et al.101 studied various K2CO3/support
ethyleneimine (PEI),110,111 dendrimers,112 hyperbranched amino-
composite materials and concluded that the host matrix should
silica,113 etc. In general, multi-amine-containing molecules are
not be limited to an inert support and can undergo chemical
superior due to their higher amino group densities. Chang
transformations caused by an interaction with the impregnated
et al.114 observed a CO2 capture capacity of 2.4–2.7 mmol g1 at
salt.
60  C on triaminosilane/SBA-15. Sayari et al.115 obtained a value
So far the issues that should be considered for practical
of 2.65 mmol g1 at 25  C on TRI-PE-MCM-41. On a tetrae-
applications of such CO2-adsorbents include durability,
thylenepentamine (TEPA)-grafted mesocellullar silica foam
carbonation reaction rate and temperature control, and energy
(MSF), a capacity as high as 4.5 mmol g1 adsorbent was ach-
management. In addition, contaminants in flue gas such as SO2
ieved at 75  C by Liu et al.116 For polyethylenimine coated glass
and HCl will react irreversibly with Na2CO3 and must therefore
fibers, Li et al.117 observed a capacity of 4.1 mmol g1 at 30  C.
be reduced to low levels prior to CO2 capture. Their practical
Liang et al.118 synthesized various generations (G0, G1, G2, G3
application is probably still a long way off.

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and G4) of melamine-based dendrimers on SBA-15. However, at reported in some grafted amines.110 The working temperature for
20  C, a CO2 capacity of only 1.0 mmol g1 (ca. 4.4 wt% g1) was CO2-capture should usually be below 60  C, with better results
observed on G3/SBA-15. On G4/SBA-15, a capacity of only achieved as the temperature approaches ambient temperature.
0.4 mmol g1 (1.7 wt% g1) was obtained instead of a theoretical For regeneration, it is usually between 120–170  C according to
value of 1.36 mmol g1 (ca. 6 wt% g1), indicating many amino our unpublished data.
groups were not accessible by the CO2 molecules. The highest
CO2 capture capacity observed was 5.55 mmol g1 on hyper-
branched aminosilica (HAS) on SBA-15 at 25  C by Hicks 3. Intermediate-temperature solid adsorbents
et al.,113 which was formed by polymerization of aziridine on (200–400  C)
SBA-15.119
Layered double hydroxides (LDHs), also known as hydrotalcite-
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Methods for loading amines onto supports can be roughly

like compounds (HTs) or anionic clays are layered basic solids.
classified as (a) impregnation, (b) post-synthesis grafting and (c)
They have been widely used as adsorbents, ion exchangers, base
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

direct condensation and hydrolysis methods.111 The samples

catalysts, and precursors of well-mixed oxides for various cata-
prepared by the impregnation method can have high amine-
lytic applications.124 Their structure consists of positively
loading but are not usually good in recycling. For the post-
charged brucite-like layers with charge compensating anions and
synthesis grafting method, the above mentioned grafting of
water molecules within the interlayer space.125–127 The metal
aminosilane molecules onto silica-based supports belongs to this
cations occupy the centers of the octahedral structures, whose
category, and usually takes place in anhydrous solution so as to
vertices contain hydroxide ions, and the octahedrons are con-
reduce the self polymerization behavior of the aminosilane
nected by edge sharing to form an infinite sheet (Fig. 4A). The
molecules.120 In the direct condensation and hydrolysis method,
general formula of the compounds is [M2+1-xM3+x(OH)2][An]x/n$
an aminosilane, a surfactant (template) and the silica precursor
zH2O, where M2+ and M3+ are divalent (Mg2+, Zn2+, Ni2+, etc.)
are mixed and reacted directly, and the amino groups can thus be
and trivalent cations (Al3+, Ga3+, Fe3+, Mn3+, etc.) respectively,
incorporated into the matrix of the synthesized material. In
An is a non-framework charge compensating anion (CO32, Cl,
a recent work by Tang et al.,121 bis((triethoxysilyl)propyl) eth-
SO42, etc.) and x is normally between 0.2–0.4. In general, LDH
ylenediamine (BTEPED) was incorporated into a porous silica
materials possess both high surface area and abundant basic sites
and a CO2 capture capacity of 2.3 mmol g1 was obtained. The
at the surface, which are favorable for adsorbing acidic CO2.128–130
materials synthesized by this method should maintain their
Fresh LDH itself does not possess any basic sites. Upon
amines well; however, not all of the amino groups are accessible
thermal treatment, LDH gradually loses interlayer water, then
to CO2 molecules as they are trapped in the silica matrix. In
addition, in many cases it is still a challenge to incorporate amine
molecules while forming the porous structure, and the uncalcined
silica wall should have a poorer hydrothermal stability than the
calcined porous silica used in the post-synthesis grafting.
The chemistry of grafted amines with CO2 is similar to that
between amines in aqueous solution and CO2.122 Three kinds of
carbonates can be formed from primary amines as shown in
Scheme 2. From the reaction pathway in Scheme 2, it is under-
standable that the existence of H2O can lead to the formation of
bicarbonate and carbonate and consume more CO2 molecules,
thus increasing the CO2 capture capacity. This is the reason why
these CO2-adsorbents can tolerate moisture; indeed, the presence
of moisture can promote the CO2 capture.110 Since these reac-
tions can run at a fast rate, the CO2-capture process is also fast,
unless the CO2 concentration is very low.
The thermal stability of amines is well studied. Degradation of
aqueous alkanolamines occurs below 140  C under atmospheric
pressure,123 though a slightly higher temperature has also been

Fig. 4 (A) Schematic structural representation of LDHs; M2+ and M3+

represent divalent and trivalent cations. (B) The structural evolution of
Scheme 2 CO2 reaction pathway with a primary amine.110 Mg-Al-CO3 LDH as a function of temperature.131

48 | Energy Environ. Sci., 2011, 4, 42–55 This journal is ª The Royal Society of Chemistry 2011
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dehydroxylates and decarbonates to a large extent, leading to the determined by the amount of low coordination number oxygen
formation of a mixed oxide with a 3D network. The detailed sites in the Mg(Al)Ox nanoparticles, which was highest on sup-
structural evolution of Mg-Al-CO3 LDH as a function of ported LDHs due to the high distribution.
temperature was investigated by Yang et al.,131 as shown in More work on modifying the composition of Mg-Al-CO3 has
Fig. 4B. Ram Reddy et al.132 reported the effect of calcination also been carried out by either substituting the CO32 anion or
temperature on the CO2 adsorption capacity of Mg-Al-CO3 Mg2+ divalent cations. Hutson et al.147 investigated CO2
LDH. The sample calcined at 400  C showed the highest adsorption on various LDHs with different anions including
adsorption capacity, which is presumably due to the trade-off CO32, Fe(CN6)4, Cl and ClO4, and concluded that Mg-Al-
between the surface area and availability of active basic sites. CO3 has the highest basic site density (692 mmol g1). Lwin
This amorphous phase has a relatively high surface area and et al.148 and Wang et al.149 studied various LDHs with different
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exposes sufficient basic sites on the surface. These basic sites divalent cations including Mg2+, Co2+, Ca2+, Cu2+, or their
favor reversible CO2 adsorption in a form as shown in reaction combinations, and came to the conclusion that the Ca–Co–Al
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

(4).133 The interaction between the adsorbed CO2 and the basic system had the highest CO2 adsorption capability. Yavuz et al.150
sites is stronger than that in the case of zeolite (see section 2.2) demonstrated that the CO2 capture efficiency could be markedly
but weaker than that in the case of alkali metal oxide (see section improved by partially substituting Al with Ga. With 10 mol%
4), which explains why the working temperature of LDH-based substitution for Al, the CO2 capture capacity increased from 0.47
CO2-adsorbents used in flue-gas systems falls in the middle to 1.40 mmol g1 for K2CO3-promoted Mg-Al-CO3. Recently,
temperate range of 200  C and above. Normally the regeneration our group has carried out a systematic investigation on the Mg-
temperature is around 400  C.132–135 M-CO3 (M ¼ Al, Fe, Ga, Mn) LDHs for the effect of trivalent
cations on their CO2 capture performance and found that the
Mg–O + CO2 / Mg–O/CO2(ad) (4) M3+ cations actually determine the structure evolution of the
LDH derivatives under the thermal treatment, and ultimately
The relatively low CO2 adsorption capacity is a problem for influence the CO2 capture capacity. A very different calcination
LDH-based adsorbents. Intense efforts have been put into temperature is required for each LDH to obtain the maximum
improving the capacity, especially on the mineral Mg-Al-CO3 CO2 capture capacity. The optimal calcination temperatures are
LDH and its derivatives. For instance, the synthetic condi- as follows: Mg3Al1 (400  C) > Mg3Ga1 (350  C) > Mg3Fe1
tions,136 presence of SOx and H2O,133,137 operation pres- (300  C) > Mg3Mn1 (250  C).151 Scheme 3 lists the possible
sures,127,138,139 alkali (K, Cs) doping,140–143 particle size,144 and the methods for modifying the composition of Mg-Al-CO3 LDHs.
use of supported LDHs145,146 were widely investigated. Sharma Besides the efforts made to increase the CO2 capture capacity,
et al.136 obtained the optimized synthetic parameters: 37% Al a more important issue is to enhance the long-term stability of
content, room temperature addition of magnesium and LDHs during CO2 adsorption/desorption cycling operation,
aluminium precursors, aging at 65  C for 18 h, and drying at which is crucial for the development of practical applications.
room temperature. A maximum CO2 adsorption of 0.98 mmol Though there is still no clear answer from the literature, the
g1 was obtained. However, it should be noted that, in their solution probably lies in the progress in materials science, either
work, the CO2 adsorption isotherms were measured at 30 and by modifying the current LDHs, or by identifying new systems.
60  C, and not in the high temperature range (200–400  C). Ram Magnesium oxide is another CO2-adsorbent working in the
Reddy et al.133,137 reported that the presence of water in the feed intermediate temperature range from room temperature up to
gas had a positive effect on the CO2 adsorption capacity, which 200  C.152 However, due to its moderate CO2 adsorption capacity
increased from 0.61 mmol g1 to 0.71 mmol g1, whereas the and poor thermal stability during regeneration, the practical
presence of SO2 had a negative effect, as it could competitively application of MgO as a CO2-adsorbent may be limited. Gregg
interact with the CO2 adsorption sites. The operation pressure et al.153 tested the CO2 capture on MgO at 200  C, and obtained
has been proven to have a significant effect: CO2 adsorption a capacity of only 0.43 mmol g1. Bhagiyalakshmi et al.154 noted
capacity increases with increasing operation pressure.127,138,139 that the complete desorption of adsorbed CO2 could only be
Doping alkali metal carbonates in LDHs is an effective approach accomplished by prolonged heating at 450  C.
to improving the CO2 adsorption. Oliveira et al.140 reported that
the adsorbed CO2 on MG 30 (commercial hydrotalcite from
Sasol, Germany) increased from < 0.1 mmol g1 to 0.76 mmol g1
after doping with K2CO3. Walspurger et al.143 investigated the
K+ promotion mechanism, and suggested that potassium ions
could strongly interact with aluminium oxide centers in hydro-
talcite, resulting in the generation of basic sites that were able to
reversibly adsorb CO2 at high temperatures. Meis et al.146 studied
the support and size effects of activated hydrotalcites for pre-
combustion CO2 capture, and found that the CO2 adsorption
capacity significantly increased with a decrease in the particle
size. The adsorption capacity of carbon nanofiber supported
hydrotalcites increased by an order of magnitude (1.3–2.5 mmol
g1) compared to that of unsupported hydrotalcites. It was Scheme 3 The possible approaches to modifying the composition of
proposed that the CO2 adsorption capacities of LDHs were Mg-Al-CO3 LDH.

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4. High-temperature solid adsorbents (> 400  C) atmosphere at high temperature (e.g. 1000 or 1100  C for 6 or
24 h) is another option and was first studied by Lysikov et al.171 in
4.1 Calcium based adsorbents 2007. Later Chen et al.180 found that the activity and durability of
It is well accepted that calcium based materials are good adsor- thermally pretreated limestone and dolomite were greatly
bent candidates for capturing CO2 due to their high reactivity enhanced. Manovic et al.172 proposed a pore-skeleton mechanism
with CO2, high capacity and low material cost.155 The reversible to explain the thermal pre-activation. The cycling stability could
reaction between CaO and CO2, as shown in reaction (5), offers also be improved by incorporating inert materials such as
a great potential for reducing CO2 from various clean energy MgO,170,181,182 CaTiO3,183 Ca12Al14O33,184–187 ZrO2,188 etc. One
systems, e.g. pre-combustion carbon capture from gasification practical problem of this method is the presence of a large
processes and post-combustion carbon capture from zero emis- amount of undesirable inert material in the adsorbent, since this
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sion coal (ZEC) processes. The carbonation temperature for will increase the capital and operating costs. Some researchers
CaO-based adsorbents is between 600–700  C and the regener- have attempted to synthesize CaO from nano-sized CaCO3
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

ation temperature is normally above 950  C.6,156–160 particles155 or organometallic precursors.189 It would make
economic sense to use cheap natural adsorbents (e.g. limestone)
and to sell the spent adsorbent to the cement industry.177,190–193
CaO(s) + CO2(g) 5 CaCO3(s),
DH 873.15 K ¼ 171.2 kJ mol1 (for carbonation) (5)
4.2 Alkali ceramic based adsorbents
Alkali metal (Li, Na, K, etc.) containing ceramics are another
This carbonation reaction is highly exothermic and it is possible to type of high temperature CO2-adsorbent. In 1998, Nakagawa
efficiently recover the large amount of energy released during the CO2 and Ohashi first reported the capture of CO2 using Li2ZrO3 at
capture. Preliminary economic analyses suggest that this process is high temperatures (400–600  C).194 This material has great
economically attractive because limestone (CaCO3) is abundant and potential because it has an excellent CO2 sorption capacity
low-cost when used at the industrial scale.161–163 The CO2 capture (28 wt%) as well as a small volume change during the CO2
reaction is characterized by an initial rapid and kinetically-controlled sorption/desorption cycles.195 The reaction and process are
phase, followed by an abrupt transition into a slower diffusion- described by reaction (6), which can occur mainly due to the
controlled phase, whereas the CO2 release reaction is much faster and lithium mobility in the ceramics (Fig. 5).196,197 During the CO2
always goes to completion in minutes. In practical applications, this sorption, the lithium atoms diffuse from the core of the particles
reaction is always carried out at temperatures $ 850  C in order to to the surface and react with CO2 to form Li2CO3, and the
produce a nearly pure stream of CO2.164–166 diffusion of CO2 in the solid Li2CO3 that is produced is the rate-
Despite the simple chemistry involved, the main problem for the limiting step for Li2ZrO3. The reverse reaction normally happens
calcium-based materials is the loss of reversibility for the at temperatures around 750–800  C.
carbonation reaction due to the sintering of the adsorbent parti-
cles.167,168 This is caused by three major factors: the carbonation Li2ZrO3 + CO2 5 Li2CO3 + ZrO2, DH298 K ¼ 160 kJ mol1(6)
process is highly exothermic, the volume increases substantially
from CaO to CaCO3 (from 16.9 to 34.1 cm3 mol1), and the
The main obstacle for the practical application of Li2ZrO3 is
Tammann temperature of CaCO3 (533  C) is much lower than
its kinetic limitation. Various efforts have been made to improve
normal carbonation temperatures.167,169,170 Lysikov et al.171
its CO2 capture performance. Nair et al.198 carried out
proposed a simple schematic diagram for the textural trans-
formation of the CaO adsorbent in recarbonation–decomposition
cycles. The first decomposition of the calcium carbonate produces
highly dispersed, nanosized CaO particles that are highly reactive.
The following carbonation is incomplete due to the slow diffu-
sion-controlled reaction with CO2 and pore blocking upon
carbonation.6 The amount of unreacted CaO and its particle size
increase from cycle to cycle until a rigid interconnected CaO
skeleton is formed. This rigid backbone is considered a much less
reactive adsorbent compared to the highly dispersed CaO. There
are some other restrictions to such processes related to the kinetics
and thermodynamics of the reactions, along with undesirable side
reactions such as sulfation and processes such as attrition.172–174
Numerous efforts have been undertaken to enhance the
durability of CaO-based CO2-adsorbents. Hydration is currently
considered to be a promising approach to reactivating the spent
adsorbents for CO2 capture.6 Manovic et al.175 and Fennell
et al.176,177 observed that the reactivity of the spent adsorbents
could be doubled following hydration. The mechanism of reac-
tivation by hydration appeared to be through breakup of parti- Fig. 5 Proposed mechanism for CO2 sorption (a) and desorption (b) on
cles to increase porosity.178,179 Thermal pre-activation in an inert Li2ZrO3.197

50 | Energy Environ. Sci., 2011, 4, 42–55 This journal is ª The Royal Society of Chemistry 2011
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a systematic study of the properties of lithium zirconates with 5. Catalytic applications of solid CO2-adsorbents
different crystal structures. They compared the properties of
three Li2ZrO3 powder samples: one commercial and two others The captured and concentrated CO2 can be catalytically con-
prepared by the solid-state reaction method and the sol–gel verted to various chemical products, e.g., to methanol via
method, and found that small particle size and tetragonal phase hydrogenation of CO2/CO,211 to syngas (H2 + CO) via drying
are crucial for enhancing the performance in CO2 capture. Later, reforming of CH4 with CO2,212 and to many fine/pharmaceutical
Ochoa-Fernandez et al.199,200 successfully synthesized nano- chemicals, etc.213 However, here we only focus on some sorption-
crystalline tetragonal Li2ZrO3 by a novel soft-chemistry route enhanced reactions that utilize the CO2-capture function of
and achieved improved kinetics. the solid CO2-adsorbents. Besides the CO2-capture capacity, the
Another method is to substitute or partially substitute Li+ by kinetics and recycling ability of the materials and the tempera-
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Na+ or K+. L opez-Ortiz et al.201 found that Na2ZrO3 achieved ture gap between the reaction temperature and the sorption/
a superior CO2 capture ability than Li2ZrO3. Pfeiffer et al.196 desorption temperature should also be considered. It is better if
the temperature gap is small; if not, in some cases it could be
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explained that Na2ZrO3 has a lamellar structure and the sodium

atoms are located among the ZrO3 layers with higher mobility. overcome by a proper combined configuration of the catalysts
On the other hand, Li2ZrO3 has a much more packed structure, and the CO2-adsorbents. Otherwise, the extra energy consump-
which limits lithium diffusion. Later lithium–sodium and tion and cost have to be considered.
lithium–potassium metazirconate solid solutions (Li2-xNaxZrO3 Several important CO2-sorption enhanced reactions are
and Li2-xKxZrO3) were also investigated.196,202,203 Pfeiffer et al.196 steam reforming (SR) of hydrocarbons or biomass-derived
found that LiNaZrO3 presented the best ability for CO2 chemical chemicals, such as glycerol,214 the water gas shift (WGS)
adsorption, exhibiting a CO2-adsorption capacity of 4.45 mmol reaction, and preferential oxidation (PROX) of CO in H2. In
g1 at 600  C, which means an efficiency of 75.3% (the efficiency general, these reactions are related to the production of H2-
is defined as the ratio between the real adsorption capacity to the rich gas. The enhanced-WGS reaction has been tested in the
theoretical value). Furthermore, LiNaZrO3 adsorbed CO2 faster pre-combustion process to clear up flue gas of the coal-fueled
than any other similar ceramics in short time spans. Veliz-Enri- gasification power plants,156,215,216 and the PROX reaction is
queza et al.203 found that Li2-xKxZrO3 solid solutions adsorbed used to produce very pure H2 (the CO concentration is
CO2 between 450 and 730  C, but the ceramics containing required to be less than 100 ppm or even 10 ppm) that can be
potassium adsorbed CO2 at higher temperatures. The kinetic fed to polymer electrolyte membrane fuel cells (PEMFCs). It
analyses indicated that Li2-xKxZrO3 solid solutions can adsorb is very common for several reactions to occur simultaneously
CO2 up to five times faster than Li2ZrO3 in short time spans. in a single reaction process, thus increasing the complexity for
Besides zirconates, some other alkali-metal-containing mate- very good control of it. For thermodynamic analyses and
rials including lithium orthosilicate (Li4SiO4),204–207 Na2SiO3,208 process considerations of some reactions and processes,
CaSiO3,209 and lithium cuprates (Li2+xCuO2+x/2)210 are also readers can refer to Harrison’s review paper and references
potential high temperature CO2-adsorbents. However, it seems therein.156 However, we should keep in mind that the effect of
there are still many undiscovered materials in this area, thus CO2 removal is not just limited to these reactions. Theoreti-
a systemic investigation is necessary. cally, a reaction having CO2 as a product could be impacted
Table 1 summarizes the general CO2 adsorption capacities of by removal of CO2.
the main types of adsorbents mentioned in this paper. However, The SR reactions usually take place above 500  C, so high-
it is worth mentioning that, once a higher adsorption pressure is temperature CO2-adsorbents are often used in these reactions.
applied, the CO2 adsorption capacity might greatly exceed the For the SR reaction of methane, CaO and Na2ZrO3 exhibit
capacity range listed in this table. This phenomenon is especially the highest reaction kinetics among various CO2-adsorbents
significant for low temperature CO2-adsorbents. For instance, (CaO, Li2ZrO3, K-doped Li2ZrO3, Na2ZrO3, and Li4SiO4).
Millward et al.67 reported that the amount of adsorbed CO2 However, the former is easily sintered thus losing its capacity
could be as high as 33.5 mmol g1 at 35 atm. gradually.217 Because of the relatively low reaction kinetics on

Table 1 The general CO2 adsorption capacities of the main types of adsorbents

Adsorption Adsorption CO2 adsorption

Adsorbent type temperature/ C pressure/atm capacity/mmol g1 References

Low temperature Carbon based # 80 1 # 3.5 10–29

adsorbents Zeolite based # 100 1 # 4.9 34–59
MOF based # 100 1 # 4.5 62–87
Alkali metal # 120 1 # 9.4 88–101
carbonate based
Amine based # 60 1 # 5.5 101–122

Intermediate LDH based 200–400 1 # 1.4 131–150

temperature adsorbents

High temperature adsorbents Calcium based 600–700 1 # 11.6 155–193

Alkali ceramic based 500–600 1 # 6.5 194–210

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Li2ZrO3, a long reactor and low space velocity have to be 6. Concluding remarks and outlook
used so as to reach the equilibrium composition.218 The sin-
tering of the adsorbents is not only due to the high reaction There is a growing awareness that anthropogenic CO2 emissions
temperature, but also to the even higher regeneration should be reduced as CO2 is a major greenhouse gas in the
temperature, which is over 850  C for CaO.219 In order to atmosphere. For the capture, storage and utilization of CO2,
improve the sorption-enhanced SR reaction further, adsor- solid CO2-adsorbents are widely used. These adsorbents can be
bents with lower sorption/desorption temperature are roughly classified into three types according to their sorption/
preferred, or SR catalysts that can catalyze the reaction at desorption temperatures: low-, intermediate- and high-tempera-
lower temperatures should be developed and applied. In the ture adsorbents with temperature ranges below 200  C, between
latter case, CO2-adsorbents that have lower sorption/desorp- 200–400  C and above 400  C respectively.
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tion temperature, e.g. LDHs, become applicable.129 (1) The low-temperature CO2-adsorbents include carbon,
The WGS reaction usually takes place between 200–500  C, so zeolites, MOFs/ZIFs, alkali metal carbonates and amine-based
materials. The first three materials adsorb CO2 mainly by phys-
Published on 21 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00064G

solid CO2-adsorbents with lower sorption/desorption tempera-

tures such as LDHs can be used. In the presence of K2CO3- ical interaction while the final two can chemically bind to CO2,
promoted LDHs, the WGS reaction on a commercial catalyst and most of them have good CO2 adsorption capacities.
could produce H2 with a CO concentration as low as 10 ppm, However, for practical applications, each of them possesses pros
because the CO conversion was increased from 99.87 to 99.999% and cons. The carbon-based materials are abundant, cheap, easy
after addition of the adsorbent.220 Van Selow et al.221 recently to make, and chemically and hydrothermally stable, but their
reported a good stability for more than 300 cycles of adsorption/ selectivity for CO2 is low in the presence of other gases (e.g. N2,
reaction and desorption on an WGS reaction system enhanced H2, CH4, etc.). Grafting functional amine groups to the carbon
by a LDH-based CO2-adsorbent, and the CO concentration was surface is a good option to solve this problem. Both zeolites and
kept at ca. 300 ppm, a value much lower than that of the MOFs/ZIFs have a high capacity for CO2 capture, and some of
conventional WGS system (usually above 1000 ppm). It should them are quite stable, but usually not cheap. The main challenge
be pointed out that in the SR reactions, the WGS reaction also for alkali metal carbonates and amine-based adsorbents lies in
often occurs, because the reformate contains CO, CO2, H2 and their long-term stability. The thermal and hydrothermal
H2O, so the existence of CO2-adsorbents enhances the two stability, especially in the presence of H2O, is a problem to
reactions.222 support materials such as mesoporous silica. It is also worthwhile
It would be ideal to combine the CO2-adsorbents with the to mention that the CO2 adsorption temperature (normally < 60

PROX reaction catalysts for fuel cell applications. After the C) of these materials is slightly lower than that of real flue gases
WGS reaction, the feed gas contains quite a low amount of CO, (normally 90  C), and the current choice is to first cool down
which allows a much longer working span for the CO2-adsor- the flue gas, which is also energy consuming. Certain modifica-
bents than that in the sorption-enhanced SR and WGS reactions. tions should be made to these materials to increase their
The PROX reaction following should be able to further lower the adsorption temperatures slightly. The amine-based solid adsor-
CO concentration significantly. Though some PROX catalysts bents have high selectivity towards CO2 and other acidic gases,
are efficient, there is limited room for further improvement of the but their capacities are still lower than that of the corresponding
selectivity for CO oxidation over H2 oxidation in a H2-enriched liquid amines. Developing amine molecules with low volatility
environment. One of the reasons is that, in the PROX process, and high density of amino groups should be a direction to
due to the generation of CO2 and H2O, the WGS and reverse pursue.
WGS reactions and even the methanation reaction may also (2) Among various intermediate-temperature CO2-adsorbents,
occur. The reverse WGS (r-WGS) reaction regenerates CO, and LDHs have been well investigated and are believed to be the most
the methanation reaction consumes H2, so both of them should promising adsorbent candidate. The main problems of this kind of
be avoided. Addition of a CO2-adsorbent is likely to shift this material are still their insufficient adsorption capacity, kinetics
WGS reaction towards H2 production and eliminate the and stability. Doping LDHs with K2CO3 can improve their
methanation reaction. From a thermodynamic viewpoint, the capacity and kinetics. For LDHs, one critical issue that cannot be
above mentioned reactions favor different reaction temperature bypassed is their stability under real operating conditions, espe-
ranges, e.g., the r-WGS and methanation reactions occur above cially during the pressure swing adsorption/temperature swing
200  C and 400  C respectively, while the WGS reaction favors adsorption (PSA/TSA) cycles and in the presence of H2O and SO2.
lower reaction temperatures. Theoretically, the enhancement will For the sorption-enhanced hydrogen production reactions, the
become more obvious for catalysts with working temperatures compatibility between LDHs and WGS/SR catalysts should also
above 200  C as the r-WGS and methanation reactions can be be considered, e.g., the temperature gap. In addition, from the
suppressed more significantly. Therefore, some catalysts with viewpoint of fundamental research, the structure of the active sites
high working temperatures may work better and become feasible for CO2 adsorption and the structural evolution of these materials
by combination with a CO2-adsorbent. Of course, the selection during the CO2 sorption and desorption are still not very clear and
of a specific CO2-adsorbent working in low, moderate or high should be further investigated.
temperature ranges is dependent on the working temperature of (3) For the high-temperature CO2-adsorbents, CaO and alkali
the selected catalyst. It is hoped that an efficient PROX process ceramics are representative materials. These CO2-adsorbents
can be developed if their working temperatures are compatible. suffer severely from textural degradation during the sorption/
Unfortunately, so far there are still no promising results reported desorption operations. Currently, these materials can only run
for this application. several tens of cycles before any obvious degradation, and are

52 | Energy Environ. Sci., 2011, 4, 42–55 This journal is ª The Royal Society of Chemistry 2011
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