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A new aerogel based CO2 adsorbent developed with a simple sol-gel method
along with supercritical drying

Article  in  Chemical Communications · August 2014

DOI: 10.1039/C4CC06424K

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A new aerogel based CO2 adsorbent developed
using a simple sol–gel method along with
Published on 26 August 2014. Downloaded by University of Wyoming on 02/09/2014 16:21:59.
Cite this: DOI: 10.1039/c4cc06424k
supercritical drying†
Received 15th August 2014,
Accepted 26th August 2014 Yong Kong,abc Guodong Jiang,abc Maohong Fan,*ad Xiaodong Shen,*bc Sheng Cuibc
and Armistead G. Russelld
DOI: 10.1039/c4cc06424k
www.rsc.org/chemcomm
A new, highly capable and dynamic aerogel adsorbent for CO2 capture
was developed using a one-step sol–gel process along with solvent
exchange and supercritical drying. The highest CO2 adsorption capacity
in a 1% CO2 flow stream (5.55 mmol g 1) is much higher than other
aerogel adsorbents obtained using a 10% or even higher CO2 gas mixture.
Aerogels are nanoporous materials with open cells, low densities,
and high surface areas and porosities.1 The microstructures and
elemental compositions of aerogels can be tailored using solution
chemistry via a process known as the sol–gel method, and have been
widely applied in various fields such as thermal insulation, catalysis,
adsorption and many other aspects.2 Recent investigations have
focused on using aerogels as new CO2 capture materials. Cui et al.
achieved a high CO2 adsorption capacity in a 10% CO2 + N2
mixture gas using amine-modified silica aerogel, rendering a
CO2 adsorption capacity at 50 1C with and without water vapor of
1.19 and 3.81 mmol g 1, respectively.3 Begag et al. developed
hydrophobic and stable amine-functionalized aerogels by grafting
amine groups onto a hydrophobic silica backbone, achieving
1.43 mmol g 1 CO2 adsorption capacity in simulated flue gas.4
Linneen et al. found that 1 g of silica aerogel immobilized with
tetraethylenepentamine (TEPA) could achieve the largest capacity
of 6.1 mmol g 1 in pure CO2 while also attaining 3.5 mmol g 1
under a dry 10% CO2 + Ar stream.5 Wang et al. found that 1 g of
a
Department of Chemical and Petroleum Engineering, University of Wyoming,
Laramie, WY 82071, USA. E-mail: mfan@uwyo.edu; Tel: +1-307-766-5633,
+1-404-385-4577
b
College of Materials Science and Engineering, Nanjing Tech University,
Nanjing 210009, PR China. E-mail: xdshen@njtech.edu.cn;
Fax: +86-25-8322-1690; Tel: +86-25-8358-7234
c
State Key Laboratory of Materials-Oriented Chemical Engineering,
Nanjing Tech University, Nanjing 210009, PR China
d
School of Civil and Environmental Engineering, Georgia Institute of Technology,
Atlanta, GA 30332, USA. E-mail: mfan3@mail.gatech.edu; Tel: +1-307-766-5633,
+1-404-385-4577
† Electronic supplementary information (ESI) available: Details of sample pre-
paration and characterization, the CO2 capture method and typical CO2 adsorp-
tion profiles, the calculation method of the CO2 adsorption capacities, and
supplementary figures. See DOI: 10.1039/c4cc06424k
This journal is © The Royal Society of Chemistry 2014
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silica aerogel can adsorb 3.3 mmol CO2 from pure CO2 at 25 1C
and 1 atm.6 Masika developed a carbon aerogel with a high
surface area of 1100 m2 g 1; however, the CO2 adsorption capacity
obtained in pure CO2 at 25 1C and 1 bar was only 2.2 mmol g 1.7
Silica aerogel membranes for CO2 capture were also developed.8
In this research, a simple one-step sol–gel process and the SCD
technique were used to develop high-efficiency adsorbents for CO2
capture based on amine hybrid silica aerogel. The effect of solvent
exchange on CO2 capture performance before performing SCD was
investigated. Depending on the solvent for solvent exchange, the
resulting samples are denoted as A-SCD-acetone, A-SCD-methanol,
A-SCD-ethanol and A-SCD-isopropanol, respectively. Moreover,
most of the CO2 capture tests of the reported porous adsorbents
were performed using gases with their CO2 volume fractions being
at least 10%, which is very favorable to the increase in CO2
adsorption capacity and the adsorption rate of any given adsorbent.9
It is easy to imagine that separation of CO2 from ultra-dilute gas
mixtures is more difficult and more expensive.10 To challenge the
resulting adsorbents prepared in this research, CO2 + N2 mixture gas
with a CO2 concentration of 1% (1% CO2 + N2 mixture gas) was used
for all of the CO2 capture tests.
N2 adsorption–desorption isotherms and pore-size distributions
are conducted to investigate the pore structure of the adsorbents
(Fig. S1, ESI†). The pore structure data of the resulting aerogel
adsorbents are summarized in Table S1 (ESI†). The surface area and
pore volume of A-SCD-acetone are the highest among all adsorbents
due to optimal intersolubility between acetone and CO2, which
favors CO2 adsorption performance. On the one hand, for a certain
element composition of a material, higher surface area leads to
higher content of the surface organic groups; on the other, high pore
volume favors gas diffusion in the pore space of the adsorbents.
The CO2 adsorption kinetics of the adsorbents prepared with
different exchange solvents are presented in Fig. 1. A-SCD-acetone
gives the highest CO2 adsorption capacity (5.55 mmol g 1), which is
understandable when the differences in surface area and pore
volume of the adsorbents are taken into account. All of the
adsorbents with different exchange solvents are based on the same
wet gel, which results in the same element composition of the
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Fig. 1 Adsorption kinetics of the adsorbents with different exchange
solvents at 25 1C (adsorption time of 20 min; adsorption gas flow rate of
300 ml min 1; weight of adsorbents: 0.10–0.11 g; 1% moisture).
adsorbents. Therefore, as the surface amine densities of the
adsorbents are the same or highly similar, higher surface area
should lead to higher surface amine content, which in turn
leads to higher CO2 adsorption capacity. Furthermore, large
pore volume also positively affects CO2 adsorption by favoring
the diffusion of mixture gas in the pore space of the adsorbent.
For further insight into differences among the adsorbents, zeta
potentials of the adsorbents were measured, with the results
summarized in Table S1 (ESI†). To the best knowledge of the
authors, this characterization method has not been used previously
for CO2 capture studies. The zeta potential of A-SCD-acetone is the
highest, indicating that the much more positively and negatively
charged ions such as RNH3+ exist within an H2O and A-SCD-acetone
mixture than within mixtures of H2O and other adsorbents. Higher
RNH3+ resulting from higher surface amine content in A-SCD-
acetone and hydrolysis of more CO2 or formation of more HCO3
leads to higher CO2 adsorption capacity. It should be noted that the
CO2 adsorption capacities obtained from the kinetic curves represent
total capacity, while the useful CO2 adsorption capacity in a practical
separation process is determined by the breakthrough point (see
ESI†). The total CO2 adsorption capacity and useful CO2 adsorption
capacity in a practical separation process is 5.55 and 3.76 mmol g 1,
respectively. Therefore, the effective fraction of adsorption capacity is
approximately 67.7%.
The CO2 adsorption kinetics of A-SCD-acetone at different
temperatures is presented in Fig. 2. The CO2 adsorption capacity of
A-SCD-acetone varies from 5.55, 5.00 to 3.97 mmol g 1 when the
adsorption temperature increases from 25, 50 to 75 1C. The CO2
adsorption behavior of A-SCD-acetone at different temperature is in
accordance with that predicted by thermodynamic theories, as CO2
adsorption by amine adsorbents is exothermic. It is notable that the
CO2 adsorption capacity obtained from A-SCD in a 1% CO2 + N2
mixture gas at a certain temperature is much higher than those
obtained from other aerogel adsorbents with 10% or even higher
CO2 gas mixtures.3–7 Except aerogel adsorbents functionalized with
amines, there are many other high-performance CO2 adsorbents.
The highest CO2 adsorption capacity of the potassium-based
adsorbents with a CO2 concentration of 1% is about 4.5 mmol g 1
at 50 1C in the presence of water vapor, which is lower than that of
A-SCD-acetone.11 Giannelis et al. reported a CO2 adsorbent based on
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Fig. 2 CO2 adsorption kinetics of A-SCD-acetone at different tempera-
tures (adsorption time of 20 min; adsorption gas flow rate of 300 ml min 1;
weight of adsorbent: 0.10 g; 1% moisture).
amine-functionalized mesoporous silica that achieved a CO2
adsorption capacity of 7.9 mmol g 1 in a 10% CO2 mixture gas
with water vapor, which is higher than that of most amine-
functionalized adsorbents, including A-SCD.12 However, their
cycling stability is poor.
Unlike CO2 adsorption capacity, the CO2 adsorption rate of
A-SCD at different temperatures seems to follow no rule, as
suggested by Fig. 3. The highest CO2 adsorption rate appears at
50 1C, which is understandable when the effects of CO2
adsorption, CO2 desorption, and the reaction activity of the
amine group are taken into consideration. Although lower
adsorption temperature leads to higher CO2 adsorption capa-
city, it should lead to a lower CO2 adsorption rate, as decreasing
temperature can result in a decrease of the reaction activity
of the amine group, according to thermodynamic theories.
Additionally, the effects of desorption should also be consid-
ered, since these become increasingly important along with the
increase of temperature. The CO2 adsorption rate of the
adsorbent depends on the competition of these factors. The
CO2 adsorption rate decreases significantly from 50 to 75 1C,
indicating that the resulting aerogel adsorbent possesses a low
desorption temperature. In later adsorption processes, 25 1C
gives a relatively high CO2 adsorption rate. This is due to the
dominant role of low temperature in favoring CO2 adsorption
capacity.
Fig. 3 CO2 adsorption rate of A-SCD at different temperatures (adsorption
time of 20 min; adsorption gas flow rate of 300 ml min 1; weight of
adsorbent: 0.10 g; 1% moisture).
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Fig. 4 Cyclic adsorption capacities of A-SCD-acetone at 25 1C (adsorption
time of 20 min; adsorption gas flow rate of 300 ml min 1; weight of adsorbent:
0.11 g; 1% moisture; weight of adsorbent: 0.10 g; desorption gas flow rate of
300 ml min 1; desorption temperature of 90 1C, 1% moisture).
As recently proposed by Jones et al. for assessing the adsorption
kinetics of CO2 adsorbents, the adsorption half time of A-SCD
(another parameter for representing the adsorption rate) must
be calculated in order to compare A-SCD with current favorable
reports of CO2 adsorbents developed for low-concentration CO2
gas mixtures.13 The adsorption half times of A-SCD-acetone at
25, 50 and 75 1C within 20 min are 1.73, 1.40 and 1.47 min,
respectively. The adsorption half times of the adsorbents pre-
pared by Jones with different air capture capacities in the range
of 0.1–2.5 mmol g 1 are more than 90 min.13 Due to differences
in CO2 concentrations, it is not possible to compare these with
A-SCD, as the adsorption half times of most adsorbents used in
low-concentration CO2 are not available even though break-
through time is given, such as with triamine-grafted pore-
expanded mesoporous silica (TRI-PEMCM-41).14 However, the
adsorption half time of TRI-PEMCM-41 in a 10% CO2 mixture
gas can be obtained, and is about 3.5 min; thus, its adsorption
half time in 1% CO2 mixture gas should be longer than 3.5 min,
i.e. longer than that of A-SCD-acetone (1.40–1.73 min). Lee et al.
developed potassium-based adsorbents and investigated their
CO2 capture performance in a mixture gas containing 1%
CO2.11 After comparing the breakthrough curves of the adsor-
bents and A-SCD, it can be seen that A-SCD has a higher
adsorption rate.
The regenerability of CO2 adsorbents is important, as this
directly affects their overall CO2 capture costs. Fig. 4 shows the
cyclic CO2 adsorption capacities of A-SCD-acetone at 25 1C. The
capacities of the adsorbent do not noticeably diminish,
decreasing only from 5.55 to 5.50 mmol g 1 after 50 cyclic
adsorption–desorption tests. This encouraging result shows
that the preparation method and its resulting adsorbent are
exceptional both in capacity and regenerability. The excellent
cycling stability of A-SCD is due to the adsorbent preparation
method. The amine group of A-SCD is from the reactant APTES,
which is fixed by the chemical bond. The amine groups of
traditional amine-functionalized adsorbents are commonly
from the surface coating layer, which is fixed by a physical
bond. Obviously, the chemically fixed amine in A-SCD is much
more robust and firm compared to the physical coating amine
in traditional amine-functionalized adsorbents.
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In summary, a simple one-step sol–gel process together
with an SCD technique can be used to synthesize a high-
performance aerogel for CO2 capture. The CO2 adsorption
capacity of the adsorbent is obviously affected by the exchange
solvent. The favorable pore structure makes A-SCD-acetone
more capable of capturing CO2, as confirmed using N2 adsorp-
tion–desorption and zeta potential characterization techniques.
The CO2 adsorption capacity of A-SCD-acetone with 1% CO2 is
much higher than those obtained from other aerogels with 10%
or even higher CO2 gas mixtures. Compared with other good
amine-functionalized CO2 adsorbents (with the exception of
aerogel adsorbent), A-SCD-acetone also has better CO2 adsorp-
tion performance. Higher CO2 adsorption capacity can be
obtained at a lower temperature because of the thermodynamic
theory, the determination of the adsorption rate by the compe-
tition of CO2 adsorption, and the CO2 desorption and reaction
activity of the amine group. Benefiting from the highly unique
properties of aerogel (e.g. high surface area and porosity, and
large pore volume), A-SCD is a dynamic adsorbent with a high
CO2 adsorption rate. Finally, the new adsorbent preparation
method is cost-effective, while the resulting adsorbent has
exceptional CO2 adsorption performance and stability.
The authors acknowledge the support of the U.S. Depart-
ment of Energy, Wyoming Clean Coal Program, and California
Energy Commission in the U.S.; and the Priority Academic
Program Development of Jiangsu Higher Education Institution
(PAPD) and the Program for Changjiang Scholars and Innova-
tive Research Team in University in China (No. IRT1146).
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This journal is © The Royal Society of Chemistry 2014