Front. Environ. Sci. Eng.
2013, 7(3): 326–340
DOI 10.1007/s11783-013-0510-7
REVIEW ARTICLE
Activated carbons and amine-modified materials for carbon
dioxide capture –– a review
Zhenhe CHEN1, Shubo DENG (✉)1,2, Haoran WEI1, Bin WANG1, Jun HUANG1, Gang YU1,2
1 State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, POPs Research Center,
Tsinghua University, Beijing 100084, China
2 Tsinghua University – Veolia Environment Joint Research Center for Advanced Technology, Tsinghua University, Beijing 100084, China
© Higher Education Press and Springer-Verlag Berlin Heidelberg 2013
Abstract Rapidly increasing concentration of CO2 in the
atmosphere has drawn more and more attention in recent
years, and adsorption has been considered as an effective
technology for CO2 capture from the anthropogenic
sources. In this paper, the attractive adsorbents including
activated carbons and amine-modified materials were
mainly reviewed and discussed with particular attention
on progress in the adsorbent preparation and CO2
adsorption capacity. Carbon materials can be prepared
from different precursors including fossil fuels, biomass
and resins using the carbonization-activation or only
activation process, and activated carbons prepared by
KOH activation with high CO2 adsorbed amount were
reviewed in the preparation, adsorption capacity as well as
the relationship between the pore characteristics and CO2
adsorption. For the amine-modified materials, the physical
impregnation and chemical graft of polyethylenimine
(PEI) on the different porous materials were introduced
in terms of preparation method and adsorption perfor-
mance as well as their advantages and disadvantages for
CO2 adsorption. In the last section, the issues and prospect
of solid adsorbents for CO2 adsorption were summarized,
and it is expected that this review will be helpful for the
fundamental studies and industrial applications of acti-
vated carbons and amine-modified adsorbents for CO2
capture.
Keywords adsorption capacity, CO2 capture, activated
carbon, amine-impregnated adsorbents
Received September 2, 2012; accepted November 1, 2012
E-mail: dengshubo@tsinghua.edu.cn
1 Introduction
Great energy demand intensifies the combustion of fossil
fuels (coal, petroleum and natural gas) with escalated
global CO2 emission. Atmospheric CO2 concentration has
reached up to 394 ppmv, which probably is the major cause
of global warming. Carbon capture and storage (CCS) is
thus becoming a very active research area motivated by
governments and scientific institutes. One important way
to control atmospheric CO2 concentration is to reduce CO2
emission from flue gas which takes up 86% of anthro-
pogenic greenhouse gas [1]. The other possibility is to
capture CO2 directly from air, and the advantages include
easy operation under ambient pure conditions and no
location limit. Table 1 lists the components and character-
istics of typical flue gas and air. Besides flue gas and air,
biogas is also a common source that contains a large
amount of CO2.
Absorption and adsorption are often used to capture CO2
from flue gas [5]. Absorption with liquid amine is most
widely applied technology for carbon capture, but there are
some obvious drawbacks such as high volatility leading to
absorbent consumption, high alkalinity causing instrument
erosion, and high energy consumption for regeneration
[6,7]. In contrast, adsorption using solid adsorbents doesn’t
have these disadvantages and exhibits promising applica-
tion for carbon capture. Solid adsorbents such as activated
carbons (AC), zeolite, metal organic frameworks (MOFs),
carbon nanotubes (CNT), alkali-metal carbonate (M2CO3),
Layered double hydroxides (LDH), metal oxide (CaO),
amine-modified materials (AMMs) are often used to
capture CO2, and their adsorption performances for CO2
are listed in Table 2.
Since flue gas and air are normally at low temperature
( < 200°C) and low CO2 pressure, some high temperature
adsorbents such as LDH, M2CO3 and CaO are not
 Zhenhe CHEN et al. Activated carbons and amine-modified materials for carbon dioxide capture 327

Table 1 Components and characteristics of flue gas and air

content/(vol. %)
sources temperature/°C pressure/bar
CO2 H2O N2 O2
flue gas [2] 3–14 6–15 73–77 3–4 50–150 ~1
air [3,4] ~0.039 1–4 78.08 20.95 – 20–40 1

Table 2 Comparison of different adsorbents for CO2 capture

adsorbent adsorption temperature/°C CO2 pressure/bar CO2 uptake/(mmol$g–1) CO2/N2 selectivity a) adsorbent cost regeneration Ref.
AC 0 1 2.8–8.6
2–15 low EEP b) [8,9]
25 1 1.5–4.8
MOFs 25 0.1 0.1–5.95
25 0.5 0.6–7.2 3–500 high EEP [10,11]
25 ≥14 6.8–54.5
Zeolite 25 1 0.75–4.66 c)
10–15 low EIP [12,13]
0 0.15 2.5–5.2
AMMs 75 1 2.0–4.95
25 0.1-0.15 0.79–14.0 – medium EEP [14,15]
25 4
10–4 1.05–1.77
LDH 200-400 0.15 <1 – low EIP [16]
M2CO3 60-100 0.1–0.15 2.0–3.0 – low EIP [14]
CaO 650-800 0.15 8–11 – low EIP [17]

Notes: a) selectivity is defined as S ¼ ðxCO2 =xN2 ÞðyN2 =yCO2 Þ, where xCO2 and xN2 are the mole fractions of CO2 and N2 in the adsorbed phase, and yCO2 and yN2 are the
mole fractions of CO2 and N2 in the bulk phase, respectively; b) energy-efficient process; c) energy-intensive process

applicable. Zeolite is attractive in terms of adsorption
capacity and cost, but water is seriously detrimental due to
the competitive adsorption of water with CO2 [18,19].
MOFs are a series of emerging microporous materials with
high specific surface areas and could be tailor-made for any
molecules in theory. However, MOFs are pretty expensive
for CO2 capture from a practical point of view, and the
uncertainty of stability under oxidation atmosphere con-
fines the MOFs research in bench scale. In contrast, AC has
highly developed pore structure, and some AC materials
possess high surface areas and pore volume, making them
have high adsorption capacity for CO2. AC has wide pore
size distribution, and the macropores and mesopores
facilitate the diffusion of CO2 within the materials,
resulting in the fast adsorption. Since the interaction
between CO2 and AC is weak, the spent AC can be easily
regenerated via vacuum swing and heating method. AC
could be prepared from cheap precursors such as nut shell
and pitch, which poses the most prominent advantage in
terms of cost over other adsorbents. In addition, AMMs
could work at a relative broad temperature range from
room temperature to 100°C. Especially, AMMs are the
only efficient materials that could capture CO2 from air at
low CO2 partial pressure. Unlike other adsorbents, the
existence of water would significantly enhance CO2
adsorption. Because of these advantages of AC and
AMMs for CO2 adsorption, we reviewed them in detail
in the following sections.
2 Carbon materials
The preparation of AC usually consists of carbonization
and activation processes. Carbonization is to remove
volatile components at high temperature while activation
is to produce the complicated pores by the reaction of
residual components with activating agents. The precur-
sors can be either fossil fuels such as coal, petroleum coke
and pitch or biomass such as wood, nut shell and bamboo,
even other materials with high carbon content such as old
clothes or tires [20,21]. Precursors, activating agents and
activating temperature in the preparation of AC all
significantly affect the adsorption behavior of CO2. The
commercial available activated carbons have low CO2
adsorption capacity due to the wide pore size distribution
and low effective pore volume [22,23]. To achieve high
CO2 adsorption on AC, lots of work has been carried out to
regulate the pore structure of AC in the preparation using
the different activation methods. Besides the conventional
activation methods, some researchers utilize the polymer
resins as the precursor, and the porous carbon material can
be obtained after the carbonization process [24]. The
328 Front. Environ. Sci. Eng. 2013, 7(3): 326–340

as-prepared carbon materials usually have low surface area as precursor to prepare AC at the KOH/C ratio of 3, the
( < 1000 m2$g–1), but the nitrogen-containing monomers adsorbed amount of CO2 on this AC was 3.5 mmol$g–1 at
could be used in the polycondensation process, obtaining 25°C and 1 bar [31], much higher than the commercial AC
the effective adsorbents for CO2 [25,26]. Template method (generally less than 2 mmol$g–1). The volume of pores < 1
is able to prepare the ordered mesoporous carbon nm was higher than other pore volume, which played an
materials, which have very narrow pore size distribution important role in CO2 adsorption. According to the above
and exhibit good sorption for CO2 [27,28]. Table 3 shows results, it is discovered that KOH as activating agent is
the adsorption of CO2 on the different carbon materials better than steam to obtain micropores or narrow
prepared by different methods, which will be discussed micropores ( < 1 nm) favorable for CO2 adsorption. Two
below. different components (DO and VR) in petroleum were
selected to obtain two mesophase pitches with different
2.1 Fossil fuel based activated carbon mesophase contents, and the mesophase pitches were
adopted as precursors to prepare AC [30]. When the
Activation method is commonly used to prepare AC, and precursor was mesophase pitch VR-5 and KOH/C ratio
CO2 adsorption on the as-prepared AC is also most was 3, the obtained AC material had the specific surface
studied. Most CO2 adsorption studies are based on the AC area of 3100 m2$g–1 and CO2 adsorption was 5.3 mmol$g–1
prepared from fossil fuels or their by-products such as coal, at 0°C and 1 bar [30]. Interestingly, CO2 adsorbed amount
coke and pitch. Shen et al. used coal tar pitch as the reached up to 8.6 mmol$g–1 (0°C, 1 bar) on the monolithic
precursor and steam as activating agent to prepare AC, and AC prepared by compressing AC powders, which is
the AC had the CO2 adsorbed amount of 1.9 mmol$g–1 at highest among all carbon materials reported. The surface
30°C and 1 bar [8]. Since the mesopore volume area of monolithic AC decreased to 2400 m2$g–1, indicat-
unfavorable for CO2 adsorption accounted for half of the ing that the surface area had no positive correlation with
total pore volume for this AC material, the CO2 adsorption CO2 adsorbed amount. During the compressing at high
capacity was not high [8]. When petroleum coke was used pressure, the size of many big pores decreased to narrow
Table 3 CO2 uptake on different carbon materials prepared by different methods
precursors preparation methods adsorption conditions CO2 uptake /(mmol$g–1) Ref.
coal tar pitch carbonization-activation(steam) 30°C, 100 kPa 1.9 [8]
coal tar pitch carbonization 25°C, 1 bar ~2.2 [29]
petroleum pitch carbonization-activation(KOH) 0°C /25°C, 1 bar 8.6/4.7 [30]
petroleum coke carbonization-activation(KOH) 25°C, 1 bar 3.5 [31]
anthracite carbonization-activation (steam) 30°C, 1 bar 1.5 [32]
carpet carbonization-activation(KOH) 25°C, 1 bar 1.9 [33]
polypyrrole carbonization-activation(KOH) 0°C,1 bar 6.2 [24]
polyacrylonitrile carbonization-activation 30°C, 4.1 MPa 11.6 [34]
graphene and polypyrrole carbonization-activation (KOH) 25°C,1 bar 4.3 [27]
eucalyptus sawdust carbonization-activation(KOH) 0°C /25°C, 1 bar 6.6/4.8 [35]
almond shell carbonization-activation(CO2) 25°C, 1 bar 2.6 [36]
olive stone carbonization-activation (CO2) 25°C, 1 bar 2.4 [37]
yeast carbonization-activation(KOH) 25°C, 1 bar 4.8 [9]
soybean carbonization-activation(ZnCl2/CO2) 30°C, 0.15 bar 0.93 [38]
resorcinol and formaldehyde carbonization 25°C, 1 bar 3.3 [39]
resorcinol and formaldehyde carbonization 25°C, 1 bar 3.1 [25]
urea and formaldehyde carbonization-activation (K2CO3) 25°C, 1 bar 1.8 [26]
melamine and terephthalaldehyde carbonization 25°C, 1 bar 3.2 [28]
phloroglucin and formaldehyde carbonization (STM a) 25°C, 800 Torr 1.5 [40]
acetonitrile carbonization (HTM b) 25°C, 1 bar 4.0 [41]
acetonitrile carbonization (HTM) 0°C /25°C, 1 bar 6.9/4.4 [42]
melamine and formaldehyde carbonization (HTM) 25°C, 1 bar 2.3 [43]
carbon tetrachloride and ethylenediamine carbonization (HTM) 25°C, 1 bar 2.9 [44]

Notes: a) soft template method; b) hard template method

 Zhenhe CHEN et al. Activated carbons and amine-modified materials for carbon dioxide capture
micropores, which may cause the increase of CO2
adsorption. In addition, the adsorption of CO2 on the
VR-5 and VR-93 at high pressure was also investigated,
and the adsorbed amount of CO2 on the VR-93 was up to
47 mmol$g–1 at 25°C and 50 bar [45], comparable with
MOFs under the same conditions. The VR-5 material had
lower sorption capacity for CO 2 than the VR-93,
suggesting that CO2 adsorption at high pressure is different
from that at normal pressure. Although fossil fuel based
ACs have high sorption capacity for CO2, fossil fuels are
unrenewable resources.
2.2 Biomass based activated carbon
Biomass as renewable resources has advantages over fossil
fuels, and it is a particularly effective way to prepare AC
using crop wastes. Plaza et al. employed olive stone as
precursor and CO2 as activating agent to prepare a series of
AC with different pore structures, and the AC had the
adsorbed amount of 2.4 mmol$g–1 for CO2 at 25°C and
1 bar [37]. The low CO2 adsorption indicated that CO2 as
activating agent was worse than KOH to prepare effective
AC for CO2 adsorption. They tried to post-modify the AC
with NH3, but the adsorbed amount of CO2 decreased to
2.0 mmol$g–1. Although it was proved that nitrogen was
introduced on the AC surface, its surface area decreased
significantly after NH3 modification, which was believed
to be the main reason for the decrease of CO2 adsorption.
Almond shell was also selected as the precursor to prepare
some AC for CO2 adsorption, and CO2 and NH3 were used
as activating agent and post-modification agent, respec-
tively [36]. The AC without NH3 modification had the
adsorbed amount of 2.6 mmol$g–1 (25°C, 1 bar) for CO2,
while the CO2 adsorbed amount on the AC after NH3
modification decreased to 1.5 mmol$g–1, similar trend with
olive nut as the AC precursor. These results indicate that
NH3 modification at high temperature is not only able to
introduce the nitrogen-containing groups, but also destroy
the pores of AC effective for CO2 adsorption. Sevilla and
Fuertes used the eucalyptus sawdust as precursor and KOH
as activating agent to prepare a series of AC at different
KOH/C ratios and activating temperature [35], and the
highest CO2 adsorbed amount reached 6.6 mmol$g–1,
much higher than other AC prepared from other biomass.
They also found that activated carbons prepared under
moderate activating condition (KOH/C = 2, 973K) had
high CO2 adsorption than that prepared under severe
activating condition (KOH/C = 4, 1073K). The surface
area of AC prepared under moderate condition was
1400 m2$g–1, while the value under severe activation
condition was 2900 m2$g–1, indicating that high surface
area didn’t represent high CO2 adsorption capacity. To find
out the relationship between the pore characteristics and
CO2 adsorption, the pore size and distribution of AC were
characterized with NLDFT model using N2 as molecular
probe. It is found that the pore size was mainly distributed
329
around 0.8 nm for the AC prepared at the KOH/C ratio of
2, while pore size was mainly around 1.2 nm for the AC
prepared at the KOH/C ratio of 4. The enlarged pores
resulted in the decrease of CO2 adsorption on the AC, and
the pore volume below 1 nm was mainly responsible for
CO2 adsorption on the AC at normal pressure [46].
Unfortunately, N2 was used in Sevilla’s research to
characterize AC, which was difficult to diffuse into narrow
micropore at 77 K and consequently resulted in the
inaccurate narrow micropore distribution. In contrast,
CO2 adsorption at 273 K is more effective than N2
adsorption at 77 K for the detection of the narrow
micropores on the premise of enough equilibrium time
[47,48]. For example, Presser et al. characterized the pore
size ( < 1 nm) distribution of a special porous carbon
material using CO2 as a probe molecule, and they
discovered that the volume of pores < 0.8 nm was
positively related with CO2 adsorbed amount (0°C,
1 bar) [46]. Therefore, they concluded that the micropores
below 0.8 nm played a dominant role for CO2 adsorption at
0°C and 1 bar [46]. Wei et al. reported that the bamboo-
based AC prepared through KOH activation had the CO2
adsorbed amount up to 7.0 mmol$g–1 at 273K and 1 bar,
and a good linear correlation between CO2 adsorbed
amount and the volume of pores < 0.82 nm was obtained,
indicating that the pores in the range of 0.33–0.82 nm were
mainly responsible for CO2 adsorption at 273K and 1 bar
[49]. KOH has been proved to be the most effective
activating agent to enhance CO2 adsorption regardless of
fossil fuel or biomass as precursors, and efforts should be
made to select suitable precursors and optimize preparation
conditions for the formation of effective pores in the
adsorbents for CO2 adsorption.
Water is found to significantly affect the CO2 adsorption
on the activated carbons. For example, the CO2 adsorption
at 25°C at the presence of water on the coconut shell based
activated carbon decreased at pressure below 1.5 MPa,
while it increased significantly at pressure above 1.5 MPa
[50]. When the yeast based activated carbon was used to
adsorb CO2, the adsorbed amount was 4.8 mmol$g–1
(25°C, 1 bar) in the presence of water, while it decreased
to 3.5 mmol$g–1 (25°C, 1 bar) when the AC was first
treated with nitrogen flow containing 3 vol.% of H2O and
then treated with CO2 flow [9]. These results indicated that
CO2 adsorption on the AC materials decreased signifi-
cantly in the presence of water at ambient pressure.
CO2 adsorption on activated carbons is very fast, and
adsorption equilibrium is usually reached within a few
minutes. Temperature has negative effect on CO2 adsorp-
tion on ACs. The AC prepared from soybean had CO2
adsorbed amount of 41 mg/g at 30°C from simulated flue
gas (15% CO2 in N2), but it decreased to 20.4 mg/g at 75°C
and even lower when oxygen was present in the gas [38].
Pevida et al. reported the CO2 adsorbed amount of 1.52
mmol$g–1 at 25°C from simulated flue gas (15% CO2 in
N2) and 0.43 mmol$g–1 at 75°C on the AC [43].
330 Front. Environ. Sci. Eng. 2013, 7(3): 326–340
Pore-filling is the main mechanism of CO2 adsorption in
the micropores of conventional AC materials, while
chemical adsorption plays an important role in CO2
adsorption on some modified ACs with nitrogen-contain-
ing groups. For the mesoporous AC, surface chemical
modification is an important method to prepare the
materials with high adsorption capacity for CO2. Nitrogen
could be introduced into pores or onto carbon skeleton of
AC materials, resulting in the enhanced CO2 adsorption.
The mesoporous carbon materials prepared by calcining
organic polycondensation polymers and template method
will be introduced in the following, and some researchers
also prepared many AC materials with high adsorption
capacity for CO2 using the nitrogen-containing precursors
[41–43].
2.3 Resin based carbon materials
Resins prepared by organic polycondensation method can
be used as AC precursor. During the polycondensation
process, nitrogen-containing monomers could be used to
prepare the nitrogen-enriched resins, and thus the prepared
AC materials contain the nitrogen-containing groups.
Drage et al. synthesized the urea-formaldehyde and
melamine-formaldehyde resins using urea and melamine
as the precursors and K2CO3 as activating agent [26]. They
found that nitrogen content was up to 12.3 wt.% for the
urea-formaldehyde resin and even 31.7 wt.% for the
melamine-formaldehyde resin. However, the AC prepared
from melamine-formaldehyde resin had the CO2 adsorbed
amount of 1.0 mmol$g–1, lower than that of the urea-
formaldehyde resin (1.8 mmol$g–1) [26]. The surface area
of AC prepared from the melamine-formaldehyde resin
(56 m2$g–1) was much lower than that of urea-formalde-
hyde resin (1283 m2$g–1), which caused the difference for
CO2 adsorption on the different AC materials. They also
found that the adsorbed amount of CO2 on the AC from the
melamine-formaldehyde resin was much higher than that
of AC from the urea-formaldehyde resin when the
adsorbed amounts were normalized with surface area,
and thus they believed that both surface chemical property
and surface areas of AC materials had contribution to CO2
adsorption.
Hao et al. added lysine during the preparation of
resorcinol-formaldehyde resin, and the resin-based carbon
material had the CO2 adsorbed amount of 3.1 mmol$g–1
(25°C, 1 bar) [25], much higher than the average
mesoporous carbon materials. The addition of lysine
into the resin could improve nitrogen content in the
prepared AC and lead to the increase of CO2 adsorption.
They also tried a series of nitrogen-containing precursors
including hexane diamine, ethylene diamine, dimethyl
amine and trimethyl amine to prepare the carbon materials,
and the carbon material prepared after the addition of
hexane diamine exhibited the CO2 adsorbed amount of
3.3 mmol$g–1 (25°C, 1 bar) [39]. It is clear that the addition
of nitrogen-containing precursors into the resins could
significantly enhance the adsorption of CO2 on the
obtained carbon materials.
2.4 Carbon materials by template method
Template method is relatively expensive for the prepara-
tion of carbon materials, and it can be classified into soft
template method (STM) and hard template method (HTM).
STM makes use of organic chemicals such as copolymers
and surfactants as templates, while HTM utilizes mesopor-
ous silica such as SBA-15, KIT-6, zeolites or silica as
templates, which can be removed to produce porous
carbon materials [51]. Carbon materials prepared by
template method would reserve the ordered pore structure
formed by templates, and the pore sizes and the functional
groups on the carbon materials could be controlled using
different templates. Nitrogen-containing organic precur-
sors can also be used to prepare the effective carbon
materials for CO2 adsorption using the template method.
Saha and Deng prepared the ordered mesoporous carbon
material by the STM [40]. Due to the use of no nitrogen-
containing precursor and the mesoporous carbon materials
obtained, the CO2 adsorbed amount on the carbon material
was only 1.5 mmol$g–1 (25°C, 1 bar), much lower than that
on the microporous AC [40]. If one wants to enhance CO2
adsorption on the mesoporous carbon materials, chemical
modification on these adsorbents should be conducted.
Pevida et al. adopted melamine as precursor and fumed
silica with sizes of 7 nm and 14 nm as template, and the
obtained mesoporous carbon materials had CO2 adsorbed
amount of 2.25 mmol$g–1 (25°C, 1 bar) [43]. Wang and
Yang selected Y zeolite and EMC zeolite as hard templates
and used acetonitrile (nitrogen-containing) and propene
(no nitrogen) as the precursors, and the ordered mesopor-
ous carbons were obtained by chemical vapor deposition
[41]. The carbon material prepared from EMC zeolite had
higher CO2 adsorption than that prepared from zeolite-Y.
The adsorbed amount of CO2 on the carbon material
prepared with acetonitrile as precursor was 4.0 mmol$g–1
(298K, 1 bar), one time higher than that with propene as
precursor. These results suggest that appropriate templates
and nitrogen-containing precursors are crucial for the
preparation of carbon materials for high CO2 adsorption.
Meanwhile, we should also notice the high cost of carbon
precursors and the complicated preparation process used in
the template method, which may prevent their application
for CO2 capture.
3 Amine-modified materials
Amine-modified adsorbents actually make use of the
amine groups grafted or loaded on the porous materials to
adsorb CO2. CO2 adsorption on these adsorbents is a
chemical process and the adsorption mechanisms mainly
 Zhenhe CHEN et al. Activated carbons and amine-modified materials for carbon dioxide capture
include: 1) under dry condition, primary and secondary
amines form carbamate with CO2 and tertiary amine works
only as proton acceptor; 2) under humid condition, amines
react with CO2 to produce bicarbonate in the presence of
water [5]. According to the difference in introduction of
amine, the amine-modified adsorbents can be prepared by
two methods. One method is to physically impregnate
amine into the porous materials, but the amines with low
molecular weights (MW) can be leached easily in the
adsorption and regeneration processes, resulting in bad
reuse performance. Another method is to chemically graft
amine onto the porous materials, and the adsorbents are
stable in the reuse process.
3.1 Amine-impregnated porous adsorbents
Xu et al. reported that the mesoporous silica (MCM-41)
was impregnated with polyethylenimine (PEI) for CO2
adsorption, and they proposed a new concept of “mole-
cular basket” to explain the relationship between porous
materials and PEI [52]. Thereafter, more and more amine-
impregnated adsorbents have been prepared for CO2
adsorption. Wet-impregnation is the most common used
method in the preparation of amine-impregnated adsor-
bents, in which amine is dissolved in volatile solvents such
as methanol and then porous materials are added for
impregnation; the adsorbents are obtained after the
evaporation of solvents.
Amines such as diethylenetriamine (DETA), tetraethy-
lenepentamine (TEPA), tetraethylenepentamineacryloni-
trile (TEPAN), pentaethylenehexamine (PEHA), 2-
amino-2-methyl-1,3-propanediol (AMPD), 2-(2-ami-
noethylamino)ethanol (AEAE), and PEI are often used
for impregnation. Since the amines with low molecular
weights have the advantages of low viscosity, high content
of primary and secondary amine groups, they are easily
loaded into the materials and the obtained adsorbents
normally have high sorption capacity for CO2, but these
amines are prone to be losing due to their high volatile
property. In contrast, PEI molecules are more stable in the
porous materials and the PEI-modified adsorbents have
stable CO2 adsorption. Therefore, more researchers are
focusing on the PEI-modified adsorbents for CO2 capture,
while the small amine molecules are hardly selected in the
preparation of amine-modified adsorbents for CO2. The
key issue to prepare the PEI-impregnated adsorbents is to
increase the effective amine content in the porous
materials, which is accessible to CO2 during the adsorption
process. We only reviewed the PEI-impregnated adsor-
bents for CO2 adsorption in this section.
Porous materials such as mesoporous silica, macropor-
ous resin and mesoporous alumina have been used as
supports to impregnate PEI for CO2 adsorption. The
desired porous materials should possess hierarchical pore
structure. The relative small pores within appropriate range
331
should have large pore volume and can load more PEI,
while the large pores could serve as pathway for PEI
diffusion during the impregnation process and facilitate
CO2 transfer and diffusion in the adsorption process. In
addition, porous materials are better in the form of
monolith or pellets so that they could be used in adsorption
beds. Table 4 listed the PEI-impregnated adsorbents for
CO2 capture in the literature, and they will be discussed
below.
3.1.1 PEI-impregnated porous silicas
Common mesoporous silicas include MCM-41, SBA-15,
mesocellular silica foams (MCF), hierarchical mesoporous
silica (HMS), mesoporous hollow silica spheres (MHS),
ordered mesoporous alumina (Meso-Al2O3), fumed silica
(F-silica) and precipitated silica (P-silica). When MCM-41
was loaded with linear PEI using the wet-impregnation
method, the adsorbed amount of CO2 was 3.02 mmol$g–1
(75°C, 1 bar) [52]. In general, the pore size of MCM-41 is
in the range of 2 nm to 4 nm. Recently, the pore-enlarged
MCM-41 (PMCM-41) with the pore size range of about
13 nm–15 nm was prepared, and the PMCM-41 was
loaded with linear PEI (MW = 423) [14]. The adsorbed
amount of CO2 on this adsorbent was 4.62 mmol$g–1 at
75°C and 1 bar, which was much higher than the PEI-
impregnated MCM-41 probably due to the loading of more
PEI molecules into the porous materials.
SBA-15 is a porous support material widely used with
hexagonal pore structure and pore size around 5–30 nm.
The surface area of SBA-15 could be as high as
1000 m2$g–1 with pore volume of 2.2 cm3$g–1 [68]. These
properties of SBA-15 are extremely suitable for PEI
loading. It is reported that the CO2 adsorbed amount on the
SBA-15 loaded with 55 wt.% linear PEI (MW = 423) was
3.93 mmol$g–1 [58]. The pore-enlarged SBA-15 with
trimethylbenzene or n-decane is named as mesocellular
silica foam (MCF) with two types of pores including
windows and cells, and the pore size of MCF is usually
larger than that of SBA-15. Normally, the CO2 adsorbed
amount on the PEI-impregnated MCF is not very high,
such as 3.43 mmol$g–1 (105°C, 0.5 bar) on the MCF
impregnated with PEI (MW = 1200) [69], 3.5 mmol$g–1
(75°C, 0.15bar) on the MCF loaded with PEI (MW = 423)
[70], and 2.5 mmol$g–1 (25°C, 0.1 bar) on the MCF loaded
with PEI (MW = 2500) [71]. However, Yang et al. reported
that the adsorbed amount of CO2 on the uncalcined MCF
with PEI (MW = 600) was up to 4.5 mmol$g–1 (70°C,
0.1bar) [56], higher than other MCF materials impregnated
with PEI under the similar conditions. It is reported that
surfactant in the as-prepared MCF provided lots of ether
groups as proton acceptors to enhance CO2 adsorption, and
surfactant left in the channels might still preserve the
micelle structure which can act as a cage to enhance the
CO2 adsorption [56]. Moreover, surfactant could create
332 Front. Environ. Sci. Eng. 2013, 7(3): 326–340

Table 4 PEI-impregnated adsorbents for CO2 capture

porous materials PEI molecular weight CO2 uptake/(mmol$g–1) adsorption conditions Ref.
HMS a) 600 4.77 75°C, 1 bar [53]
b)
MHS 423 4.91 75°C, 0.2 bar [54]
HMS 600 4.95 75°C, 1 bar [55]
PMCM-41 c) 423 4.62/1.70 75/25°C, 1 bar [14]
d)
MCF 600 4.5 70°C, 0.67 bar [56]
Carbon black 423 3.5 75°C, 1 bar [57]
SBA-15 423 3.93/2.56 75/25°C, 0.1 bar [58]
e)
PMMA 423 2.50 25°C, 0.15 bar [59]
Meso-Al2O3 600 1.95 25°C, 0.1 bar [60]
Meso-Al2O3 600 1.74 25°C, 400 ppm [60]
Meso-Al2O3 423 1.13 25°C, 0.15 bar [61]
SBA-15 423 2.39 75°C, 0.15 bar [62]
SBA-15 600 2.93 75°C, 1 bar [63]
MCM-41 600 2.52 75°C, 1 bar [63]
f)
F-silica 25000 1.72 25°C, 0.12 bar [64]
g)
P-silica 800 3.34 70°C, 1 bar [65]
P-silica 25000 2.95 70°C, 1 bar [65]
GF h) 25000 4.12 30°C, 0.24 bar, humid [66]
GF 25000 2.02 30°C, 0.16 bar, humid [67]

Notes: a) hierarchical mesoporous silica; b) mesoporous hollow silica spheres; c) pore-enlarged MCM-41; d) mesocellular silica foams; e) poly(methyl methacrylate); f)
fumed silica; g) precipitated silica; h) glass fiber

extra CO2 pathways and facilitate the CO2 diffusion into
deeper polymer amine films. Consequently, the surfactant-
promoted adsorbents offered increased amount of reactive
sites and high utilization efficiency of amine groups for
CO2 capture, leading to an enhanced CO2 capture capacity
[55]. In addition, the window and cell sizes of the MCF
were reported to be 20 nm and 16 nm, respectively [72],
while the cell size of normal MCF is usually larger than 30
nm and window size is smaller than 10 nm. The
homogeneous size distribution of windows and the cells
inside the MCF facilitated the PEI loading and CO2
adsorption.
Smått et al. prepared the HMS with the pore sizes mainly
distributed at about 4 nm and 17 nm [73], which was a
perfect porous material for the preparation of CO2
adsorbents using the impregnation method. The pores at
the size of 4 nm could serve as “molecular basket,” while
the pores at the size of 17 nm could act as both PEI
pathway during the impregnation process and CO2
diffusion pathway during the adsorption process. Chen et
al. used the HMS as support to load 65 wt.% PEI, and the
obtained adsorbent had the CO2 adsorbed amount of 4.77
mmol$g–1 (75°C, 0.1atm) [53]. Wang et al. studied the
influence of surfactants on the adsorption of CO2 on the
PEI-impregnated HMS, and it is found that the surfactants
could create diffusion pathways for CO2 and consequently
more amine groups could adsorb CO2 [55]. The CO2
adsorbed amount on the HMS loaded with 65 wt.% PEI
(MW = 600) was around 4 mmol$g–1, and the value
increased to 4.95 mmol$g–1 after the addition of 5 wt.%
Span-80 surfactant during the PEI loading process.The
MHS is a kind of mesoporous silica in the form of hollow
spheres with mesoporous wall, where the hollow structure
could serve as storage and the mesoporous wall structure
could provide large surface area for reaction and also act as
pathways for small molecules. The MHS has the broad
application in some fields such as catalysis, separation,
sensing, and drug delivery [74]. Qi et al. impregnated the
MHS with linear PEI (MW = 423), and the CO2 adsorbed
amount was up to 4.91 mmol$g–1 (75°C, 0.2 atm) [54]. The
high CO2 uptake was attributed to high PEI loading and
exposure of active amine sites by channels around wall of
MHS. Comparing with adsorbents based on the HMS and
MHS, they possessed the common characteristics for
storage (4 nm pores for HMS and hollow cell for MHS)
and CO2 diffusion pathways (17 nm pores for HMS and
mesopores on the wall of MHS). The multi-type of pores
seems to be effective for PEI loading and CO2 adsorption.
Some pores work as PEI holder, and others are PEI and
CO2 diffusion pathways. Large pore volume is required to
load as much PEI as possible, and the pore size should be
suitable for CO2 diffusion. The pore size of 17 nm is
acceptable but pores above 350 nm would lead to poor
amine efficiency [53–55].
 Zhenhe CHEN et al. Activated carbons and amine-modified materials for carbon dioxide capture
Based on the above studies, the effects of PEI molecular
weights and the pore characteristics of the porous materials
on CO2 adsorption on the PEI-impregnated adsorbents are
illustrated in Fig. 1. The materials with larger pore sizes
usually contain higher pore volume to load more PEI,
resulting in higher CO2 adsorption. The CO2 adsorbed
amounts on the PEI-impregnated materials follow the
order of PMCM-41 > SBA-15 > MCM-41. For pore
structure, 3-dimension and multi-types of pore structures
are usually better than unidimensional single pore
structures due to easy diffusion of both PEI during
impregnation process and CO2 during adsorption process.
The loading PEI molecular weights also affect the CO2
adsorption on the PEI-impregnated materials, and CO2
adsorbed amounts increase with decreasing PEI molecular
weights, but the PEI with low molecular weights is easy to
evaporate in the adsorption and desorption processes.
CO2 adsorption kinetics curve on the amine-impreg-
nated adsorbents could be divided into three segments
including initial, intermediate, and final adsorption. Yue
et al. measured CO2 adsorption kinetics on the amine-
impregnated MCM-41 and SBA-15 [75,76], and 1.5 min
was required to reach half of equilibrium capacity for the
amine-impregnated MCM-41 while adsorption still
occurred at 140 min. For the amine-impregnated SBA-
15, it took 2 min to reach 75% of CO2 sorption capacity at
150 min. The ultra long time to reach equilibrium is not
Fig. 1 Effects of PEI molecular weights and the pore characteristics of the porous materials on CO2 adsorption on the PEI-impregnated
adsorbents
333
acceptable for actual application, and thus the adsorbents
with fast CO2 adsorption are preferable. Heydari-Gorji et
al. studied the effect of the pore length on CO2 adsorption
on the amine-modified SBA-15 [58], and it was found that
the SBA-15 platelet with the shortest pore length had
fastest adsorption of CO2, indicating that short pore length
decreased CO2 diffusion resistance. To enhance the
adsorption kinetics, the PEI aggregates inside pores should
be controlled, and thus more PEI molecules can be
available for CO2. Yan et al. studied the adsorption kinetics
of CO2 on the PEI impregnated MCF and found that the
second-order model described CO2 adsorption well.
Meanwhile, the adsorption rate obviously decreased with
an increase in the quantity of impregnated PEI [56].
Since the formation of carbamate or bicarbonate during
the adsorption of CO2 on amines is exothermic process, the
adsorbed amount of CO2 on amine-modified adsorbents
decreases with the increase of temperature. However, CO2
adsorption on some PEI loaded porous materials increases
with increasing temperature and reaches the highest value
at 75°C [14,52]. The reason is that the PEI molecules exist
in the channels like nanosized particles and the adsorption
sites inside the PEI particles will be subject to the diffusion
limitation at low temperature, while CO2 is easier to
contact more affinity sites on PEI chains at high
temperature [14,52,56]. Of course, high temperature is
not favorable for CO2 adsorption if the amines on the
334 Front. Environ. Sci. Eng. 2013, 7(3): 326–340
adsorbent surface have the main contribution to the
adsorption capacity.
Although the PEI-impregnated materials have high CO2
adsorption capacity, they are limited in laboratory-scale
and are too expensive to be applied in industry-scale. In
contrast, the fumed silica (aerosol 380) prepared by
chemical vapor deposition method is much cheaper than
the mesoporous materials. Goeppert et al. impregnated the
fumed silica with PEI (MW = 25000) to adsorb CO2 from
air [64], and the CO2 adsorbed amount was 1.77 mmol$g–1
under humid condition (25°C), a little higher than that
obtained under dry condition. The adsorbent could be
regenerated under vacuum because the PEI with a
molecular weight of 25000 is not volatile. Aerosol 380 is
a superfine powder with 7 nm diameter, and the fine
particles facilitate the CO2 diffusion and mass transfer
during adsorption process, which could be one of the
important reasons for the high adsorption at the ultra-low
CO2 concentration. Besides the fumed silica, they also
adopted the precipitated silica (P-silica) as the porous
material to load PEI for CO2 adsorption [65]. Two kinds of
PEI with the molecular weights of 800 and 25000 were
tested, and their corresponding adsorbed amounts for CO2
were 3.34 and 2.95 mmol$g–1 (70°C, 1 bar). Besides the
HMS and MHS, the P-silica impregnated with PEI
presented higher CO2 adsorption than other PEI-loaded
mesoporous materials such as MCM-41 and SBA-15. The
P-silica had a surface area of 124 m2$g–1 and pore volume
of 0.74 mL$g–1, which were much lower than those of
SBA-15 and MCM-41, and thus the surface area and pore
volume would not dominate the CO2 adsorption on the
PEI-impregnated adsorbents. The average pore size of P-
silica was around 10 nm with a pretty narrow size
distribution, indicating that the larger pore sizes than
SBA-15 and MCM-41 facilitated the PEI loading and CO2
adsorption. Since the P-silica could be prepared by the
simple reactions with pretty low cost in comparison with
the mesoporous silica, the practical application of PEI-
impregnated P-silica is possible. Generally, the PEI-
impregnated silicas are the promising adsorbents for
carbon capture from flue gas and air because of their
compatibility with water and high adsorption capacity at
low CO2 partial pressure. However, most mesoporous
silicas are powdered materials which are not suitable for
packing in adsorption beds, and their high price also
retards their application.
3.1.2 PEI-impregnated porous resins
In comparison with the mesoporous silicas, macroporous
resins have relatively low pore volume and wide distribu-
tion of pore sizes, but they have the advantages of stability
at temperature below 150°C and spherical shape in
millimeter scale favorable for use in adsorption beds.
Gray et al. loaded the poly(methyl methacrylate)
(PMMA) microspheres with PEI (MW = 423); the CO2
adsorbed amount was about 2.50 mmol$g–1 at 25°C and
0.15 bar and this value increased by 40% percent under
humid condition [59], different from the PEI loaded carbon
black or PMCM-41. This difference may be related to the
amount of PEI loading. The lower PEI loading (40%) on
the PMMA than carbon black (50%) or PMCM-41 (55%)
may be favorable for CO2 diffusion in the presence of
water [14,57]. Li et al. adopted the layer-by-layer self-
assembly technique to load PEI and poly (sodium
styrenesulfonate) alternately inside PMMA microspheres,
and the highest CO2 adsorbed amount obtained was about
1.7 mmol$g–1 at 40°C and 1 bar [77]. In spite of low
adsorbed amount, the adsorbent had fast sorption for CO2
in comparison with other adsorbents. They would be
promising candidates for the preparation of PEI-impreg-
nated materials for CO2 adsorption if the porous resins are
optimized to load more effective PEI.
3.1.3 PEI-impregnated porous alumina
PEI-impregnated adsorbents could be regenerated with
three methods including temperature-vacuum swing, hot
CO2 flow and water vapor. PEI would form urea
irreversibly at high temperature, while adsorbents regen-
erated by water vapor (usually lower than 110°C) could
avoid this formation [78,79]. Steam at this temperature is
sometimes considered as waste steam in industrial
processes, and thus steam regeneration is more competitive
than others. However, normal mesoporous silicas such as
MCM-41, SBA-15 and MCF are proved to be unstable in
water vapor especially in the presence of alkali (PEI is very
basic in the presence of water), and CO2 adsorption
decreases dramatically after the pores of mesoporous
materials collapse. Therefore, mesoporous alumina stable
under steam was used to prepare the PEI-impregnated
adsorbent for CO2 adsorption [60], and the adsorbed
amount was 1.95 mmol$g–1 at 10% CO2 and 1.74 mmol
$g–1 at 400 ppm CO2 at 25°C. Similarly, mesoporous
Al2O3 pellets were prepared to load PEI (MW = 423), and
the CO2 adsorbed amount was about 1.13 mmol$g–1 (25°C,
0.15 bar) [61]. It is obvious that the PEI-impregnated
mesoporous alumina has lower CO2 adsorption than the
PEI-impregnated mesoporous silica. The lower CO2
adsorption is probably due to lower pore volume and less
ordered mesoporous structure which decreased PEI
loading. Further development of PEI loaded alumina
depends on the progress of mesoporous alumina with
various pores.
3.1.4 PEI-impregnated glass fiber
Li et al. reported that PEI molecules were first cross-linked
by different cross-linkers and then impregnated on glass
 Zhenhe CHEN et al. Activated carbons and amine-modified materials for carbon dioxide capture 335

fiber to prepare CO2 adsorbents [66,67]. They investigated
the adsorption performance of CO2 from simulated flue gas
(16% CO2, 84% N2, RH = 80%). When epoxy resin was
used to crosslink PEI, CO2 adsorbed amount on the
prepared adsorbent was 2.02 mmol$g–1, while CO2
adsorption increased to 4.12 mmol$g–1 on the PEI-
impregnated glass fiber with epichlorohydrin as cross-
linker [66]. The effect of temperature on CO2 adsorption
on these adsorbents is different from that on the PEI loaded
mesoporous silicas. When temperature increased from
30°C to 75°C, CO2 adsorbed amount on the glass fiber
with PEI cross-linked by epichlorohydrin decreased from
3.98 mmol$g–1 to 2.9 mmol$g–1. The successful applica-
tion of nonporous glass fiber challenges the necessary use
of highly porous materials as support for PEI, and glass
fiber is also much cheaper than mesoporous silica.
3.2 Amine-grafted adsorbents
Amines are usually grafted onto porous materials via the
silane chemical reaction, coupling and polymerization
methods. Among them, silane chemical reaction is the
most common method to prepare the amine-grafted
adsorbents for CO2 adsorption. Table 5 shows the CO2
uptake on different amine-grafted adsorbents reported in
the literature.
3.2.1 Silane chemical reaction
Amine-containing silanes can be grafted onto the surface
of porous silica materials to prepare amine-enriched porous
materials for CO2 capture. In general, siloxane groups of
amine-containing silanes first hydrolyze or alchoholyze

Table 5 CO2 uptake on different amine-grafted adsorbents

porous materials amines preparation methods CO2 uptake /(mmol$g–1) adsorption conditions Ref.
PMCM-41 a) TAP b)
silane 2.8 25°C, 1 bar [80]
c)
PMCM-41 AP silane 2.05/2.70 25°C, 0.05/1 bar [81]
MCM-48 AP silane 1.14/2.05 25°C, 0.05/1 bar [82]
SBA-15 AP silane 0.65 60°C, 0.15 bar, humid [83]
SBA-15 DAP d) silane 1.51 60°C, 0.15 bar, humid [83]
SBA-15 TAP silane 1.80 60°C, 0.15 bar, humid [83]
[84]
MS e) AP silane 1.25 25°C, 1 bar
MS DAP silane 1.71 25°C, 1 bar [84]
MS TAP silane 1.74 25°C, 1 bar
[84]
MS AP silane 1.59 20°C, 0.9 bar [85]
SBA-12 AP silane 1.0 25°C, 0.1 bar [86]
SBA-15 AP silane 1.5 25°C, 0.1 bar [86]
MCM-41 TAP silane 1.41 25°C, 0.05 bar [87]
SBA-15 AP silane 0.5 60°C, 0.15 bar, humid [88]
SBA-15 DAP silane 0.9 60°C, 0.15 bar, humid [88]
SBA-15 TAP silane 1.21 60°C, 0.15 bar, humid [88]
f)
CNT DAP silane 2.59 60°C, 0.5 bar [89]
CNT AP silane 1.32 20°C, 0.15 bar [90]
g)
NFC DAP silane 1.39 25°C, 506 ppm, humid [91]
MCM-41 TREN h) coupling 1.36 25°C, 1 bar [92]
MCM-48 TREN coupling 1.59 25°C, 1 bar [92]
MS PEI coupling 0.98 30°C, 1 bar [93]
PPN-6 i) EDA j) coupling 3.25 22°C, 0.15 bar [94]
PPN-6 DTA k) coupling 4.3 22°C, 0.15 bar [94]
PPN-6 TREN coupling 3.5 22°C, 0.15 bar [94]
PPN-6 TETA l) coupling 3.25 22°C, 0.15 bar [94]
SBA-15 polyarizidine polymerizaiton 3.11 25°C, 0.1 bar [95]
SBA-15 polyarizidine polymerizaiton 5.55 25°C, 0.1 bar, humid [95]
MS polyarizidine polymerizaiton 0.47 45°C, 0.1 bar [96]
m)
MCF Mel and EDA polymerizaiton 0.89 20°C, 0.9 bar [97]
n)
PANF poly(allylamine) polymerizaiton 6.22 22°C, 0.15 bar, humid [98]

Notes: a) pore-expanded MCM-41; b) 3-[2-(2-aminoethyl) aminoethyl] aminopropyltrimethoxysilane; c) 3-aminopropyltrimethoxysilane; d) 3-(2-aminoethyl)

aminopropyltrimethoxysilane; e) mesoporous silica; f) carbon nanotubes; g) naofibrillated cellulose; h) tris(2-aminoethyl)amine; i) porous polymer networks; j)
ethylene diamine; k) diethylene triamine; l) triethylene tetramine; m) melamine; n) polyacrylonitrile fibers
336 Front. Environ. Sci. Eng. 2013, 7(3): 326–340
and then condensate with active hydroxyl groups on the
surface of porous materials. Finally a single layer of amine
groups are formed. Three most common silanes are 3-
aminopropyltrimethoxysilane (AP), 3-(2-aminoethyl) ami-
nopropyltrimethoxysilane (DAP) and 3-[2-(2-aminoethyl)
aminoethyl] aminopropyltrimethoxysilane (TAP). Many
studies have been done to prepare effective CO2
adsorbents using the methodology of silane chemistry
and several excellent results are listed in Table 5. It can be
seen that the CO2 adsorbed amounts on most adsorbents
prepared by the silane chemistry method are less than
3 mmol$g–1 at room temperature in spite of use of different
porous materials and silanes. Since the porous materials
could only provide the limited reactive and accessible
hydroxyl groups on the surface to react with silane, the
density of amine groups on the adsorbents is not high
enough to achieve high CO2 adsorption.
3.2.2 Coupling method
In this method, coupling agents are first grafted onto the
surface of porous materials and then amine-containing
compounds are then connected with coupling agents to
form amine-enriched adsorbents for CO2 adsorption. The
adsorbents prepared by coupling method usually have high
sorption capacity for CO2. Kassab et al., in 2011, attached
PEI on MCM-41 coupled by silane with epoxy group,
but obtained a pretty low CO2 adsorbed amount around
0.98 mmol$g–1 (30°C, 1 bar). The low uptake puts an end
to this adsorbent [93]. Recently, Lu et al. grafted methyl
chloride onto a porous polymer (namely PPN-6) with an
extremely high surface area, followed by grafting several
amines including ethylene diamine, diethylene triamine, tri
(2-aminoethyl)amine and triethylene tetramine on the
surfaces [94]. It is found that the PPN-6 grafted with
diethylene triamine had the highest CO2 adsorbed amount
of 4.3 mmol$g–1 (22°C, 1 bar). The amine-grafted PPN-6
adsorbents artfully made use of physical adsorption in the
micropores of PPN-6 and chemical adsorption on the
grafted amines. The main adsorption mechanism could
be chemical adsorption since the CO2 adsorbed amount
on the PPN-6 was only 1.3 mmol$g–1 (22°C, 1bar). The
trend of improvement in CO2 adsorption in terms of
tethered polyamine groups was diethylene triamine > tri(2-
aminoethyl)amine > triethylene tetramine > ethylene
diamine.
3.2.3 Polymerization method
Amine grafted adsorbents can also be prepared by the
polymerization of amine-containing monomers on the
surface or inside pores of porous materials. The as-
prepared adsorbents contain high density of amine groups
on the surfaces. Liang et al. reported the dendrimer for CO2
adsorption, which was prepared by first grafting melamine
onto the SBA-15 and then grafting ethylene diamine and
repeating the reactions [99]. The adsorbed amount of CO2
after three cycles grafting was about 1.02 mmol$g–1 (20°C,
0.9 bar) which is lower than other amine-grafted materials.
This result is probably due to the presence of arylamine
groups, which is less reactive than aliphatic amine
including primary, secondary and tertiary amines. Hicks
et al. prepared the adsorbents by grafting polyaziridine
onto the SBA-15 and named the adsorbents as hyper-
branched aminosilica (HAS) [100]. Aziridine underwent
the ring-opening polymerization catalyzed by acetic acid,
and the hyperbranched aminopolymers were covalently
bound to the SBA-15 support. Since the grafted amines
were mainly composed of primary and secondary amine
groups, HAS exhibited the CO2 adsorbed amount of
3.11 mmol$g–1 (25°C, 0.1 bar) and 5.55 mmol$g–1 under
humid conditions [95], higher than the dendrimer. They
also grafted polyaziridine onto the mesocellular foams, but
the CO2 adsorbed amount was only 0.47 mmol$g–1 (45°C,
0.1 bar). The even worse is that adsorbent was unstable
after steam regeneration, and a rapid decrease of CO2
adsorption was observed [96]. The steam instability was
observed in almost all kinds of mesoporous silicas which
underwent pore collapse after steam treatment.
A different polymerization method was reported by
Yang et al., and they first treated the polyacrylonitrile fibers
(PANF) with 60Co-γ rays and then grafted poly(allylamine)
onto the PANF surfaces [98]. 60Co-γ rays created radicals
on the surfaces of PANF and allylamine could polymerize
around PANF initiated by persulfate. The CO2 adsorbed
amount of PANF grafted poly(allylamine) reached
6.22 mmol$g–1 (22°C, 0.15 bar, humid) when the aminated
PANF contained 60 wt.% poly(allylamine).
The amine-grafted adsorbents for CO2 adsorption have
the advantages of high stability during adsorption process
due to covalent bonding of organoamine on the supporting
materials, but they have the complex preparation processes
and high preparation cost in comparison with the amine-
impregnated adsorbents. Due to the limited amine groups
on the adsorbents prepared by silane chemical reaction, the
adsorbents usually possess a moderate adsorption capacity
for CO2. In contrast, the adsorbents prepared by coupling
and polymerization methods have high CO2 adsorption
capacity since the high density of amine groups are grafted
on the adsorbent surfaces. It is clear that the PEI-
impregnated materials not only possess the relatively
high CO2 adsorption capacity but also have the simple
preparation method and low preparation cost compared
with the amine-grafted adsorbents.
4 Concluding remarks and outlook
Adsorption using solid adsorbents is one of the important
methods to capture CO2 from flue gas. Many adsorbents
 Zhenhe CHEN et al. Activated carbons and amine-modified materials for carbon dioxide capture
have been prepared and used to adsorb CO2, but they all
have advantages and disadvantages, and no ideal adsorbent
exists. Among all solid adsorbents, activated carbons and
amine-modified materials are attractive for CO2 adsorp-
tion. AC has the advantages of relatively high CO2
adsorption, low cost, various available precursors, and
easy regeneration. Amine-modified materials have the high
CO2 adsorption at low CO2 partial pressure, and the
presence of water would significantly enhance their
adsorption capacity.
Carbon materials can be prepared from a wide variety of
precursors, especially the activated carbons prepared from
biomass and fossil fuels using KOH activation have the
high sorption capacity for CO2. The addition of nitrogen-
containing precursors could significantly enhance CO2
adsorption on the obtained carbon materials. The activated
carbon prepared from petroleum pitch keeps a record of
CO2 adsorption capacity among all adsorbents at 273K and
1 bar. The biomass-derived activated carbons are more
competitive for carbon capture due to their high CO2
adsorption capacity as well as the sustainable and cost-
effective precursors. By now, only few biomass-derived
activated carbons have been prepared by KOH activation
for CO2 adsorption, and it is possible to prepare more
effective activated carbons using appropriate biomass.
Since pore-filling is the main mechanism of CO2
adsorption on AC materials, it is important to find the
relationship between micropores and CO2 adsorption.
Although some researchers have stated that the narrow
micropores below 1 nm are responsible for CO2 adsorp-
tion, more experimental results are required to support this
and make relationship more accurate. Especially, such
fundamental study will guide the preparation of highly
efficient activated carbons with satisfactory micropores for
CO2 adsorption.
Amine-modified adsorbents have the advantages of high
adsorption capacity and high selectivity for CO2, and they
particularly exhibit high CO2 adsorption at low pressure at
the presence of water. Amine-grafted adsorbents are quite
stable during CO2 adsorption and desorption processes, but
the complex reactions in the preparation increase the cost
of adsorbents. Low CO2 adsorption is one of the
limitations of amine-grafted materials prepared by silane
chemical reaction, but it is improved after the development
of coupling and polymerization methods. The simple PEI-
impregnated adsorbents are the research hot spots and
seem to be more attractive for CO2 adsorption. The
challenge is to optimize the impregnation of PEI with
different molecular weights in the porous materials with
different pore sizes during the preparation, and make more
available PEI molecules in the pores for effective CO2
adsorption.
There are still many challenges for CO2 adsorption on
solid materials. First, most adsorbents have good adsorp-
tion capacity for CO2 under the standard conditions in
laboratory, but it would become worse under the actual
337
conditions such as low CO2 partial pressure, high
temperature, the presence of water and co-existing gaseous
components. Therefore, the effective adsorbents for CO2
adsorption in specific situation should be prepared.
Second, the adsorbent cost is crucial in the application of
adsorbents in CO2 capture. The cost-effective adsorbents
with relatively good adsorption performance should be
selected and applied for CO2 capture from flue gas,
especially in developing countries. Third, all adsorbents
for CO2 capture should be evaluated in all aspects such as
adsorbent cost, adsorption capacity, adsorption velocity,
selectivity, and regeneration, and the energy-efficient
adsorbents should be applied to solve the issue of
anthropogenic CO2 emission.
Acknowledgements This research was supported by Tsinghua University-
Veolia Environnement Joint Research Center for Advanced Technology and
the National Nature Science Foundation of China (Grant No. 50838002).
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