Journal of CO₂ Utilization 21 (2017) 82–88

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Journal of CO2 Utilization

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Thermodynamics of Adsorption of Carbon Dioxide on Various Aerogels MARK

⁎
Muhammad Anas, Abdullah Göktuğ Gönel, Selmi Erim Bozbag, Can Erkey
Department of Chemical and Biological Engineering, Koç University, 34450 Sarıyer, Istanbul, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: Excess CO2 adsorption isotherms on silica, resorcinol-formaldehyde, carbon, and wheat starch aerogels at 308 K,
Aerogel 318 K, and 328 K and at pressures up to 35 bar were measured using a volumetric method. Total or absolute
absolute adsorption adsorption isotherms were calculated from experimentally obtained excess adsorption isotherms using the pore
excess adsorption volume of each adsorbent. It was found that silica aerogel with the BET surface area of 1158 m2 g−1 had a
CO2 capture
maximum absolute uptake of 14 mmol g−1 and resorcinol-formaldehyde aerogel (RFA-19) with the BET surface
high pressure
area of 620 m2 g−1 had a maximum uptake of 13 mmol g−1 at 308 K and 35 bar. CO2 adsorption isotherms for
silica, resorcinol-formaldehyde, and wheat starch aerogels were well represented with the Langmuir model
whereas isotherms for carbon aerogel were fitted with the Freundlich model. It was also found that the excess
uptake correlated well with the mesopore surface area of each aerogel at various pressures. The isosteric heat of
adorption for each aerogel was also determined from the variation of pressure with temperature at a constant
excess uptake. Among all aerogels, wheat starch aerogel had the highest value of −32.1 kJ mol−1 and carbon
aerogel had the lowest value of −17.7 kJ mol−1. Adsorption capacities of aerogels determined were comparable
with other classes of adsorbents and presents an opportunity for further investigation of aerogels as potential
materials for carbon capture especially at high pressures.

1. Introduction and aerogels [15]. A major disadvantage in using chemical sorbents is

Global warming is leading to destabilization of marine ecosystems,
increase in sea-levels, and acidification of oceans. The major cause of
global warming is the greenhouse gas, carbon dioxide (CO2), which is
primarily produced by the combustion of fossil fuels and its capture is
important to prevent the increase of concentration of CO2 in the at-
mosphere [1–3]. In addition to capturing carbon dioxide for seques-
tration, carbon capture is also of interest to natural gas industries be-
cause approximately 40% of the natural gas reserves are unexploited
due to high CO2 content and the costs associated with separating CO2
[4,5]. Therefore, there is a need for development of high performance
and cost effective carbon capture technologies. Several techniques such
as absorption, cryogenic distillation, membrane separation, and ad-
sorption are being investigated for carbon capture. Adsorption is ad-
vantageous as it is cost-effective, applicable for a wide range of tem-
peratures and pressures, and requires low energy for regeneration of
adsorbent [3,6,7].
A wide variety of adsorbents have been investigated for carbon
capture by chemisorption and physisorption at different temperatures
and pressures [6–8]. These include chemical sorbents such as metal
oxides [9,10] and various porous physical sorbents such as activated
carbon [11,12], zeolites [13], metal-organic frameworks (MOFs) [14]
difficult regeneration of the sorbent [6,7], therefore, many studies are
focused on physical sorbents. For instance, Siriwardane et al. [16] de-
termined adsorption isotherms of CO2 on activated carbon and zeolite
at 298 K and pressures up to 20 bar. At lower pressures, Zeolite 13X had
a higher adsorption capacity compared to activated carbon, however,
activated carbon had greater adsorption capacities at high pressures.
Maximum adsorption capacity was 8.5 mmol g−1 at 20 bar for acti-
vated carbon compared to 5.2 mmol g−1 for Zeolite 13X. In addition,
Cavenati et al. [17] measured high pressure CO2 adsorption isotherms
on Zeolite 13X at different temperatures and found that adsorption
capacity increased with increasing pressure with a maximum adsorp-
tion capacity of 7.4 mmol g−1 at 298 K and 32 bar. Higher capacities at
high pressures were found to be dependent on the surface area of the
materials because activated carbon had higher surface area
(897 m2 g−1) then zeolite 13X (506 m2 g−1). Moreover, Millward and
Yaghi [14] investigated different MOFs and determined maximum CO2
adsorption capacity of 35 mmol g−1 for MOF-177 at 298 K and 42 bar.
Aerogels may also be used as adsorbents for carbon capture due to
their large surface areas and tunable properties. Both inorganic and
organic aerogels are being investigated in many laboratories around the
world for a wide variety of applications including thermal insulation
and drug delivery [15,18]. A number of studies on adsorption of CO2 on

⁎
Corresponding author.
E-mail address: cerkey@ku.edu.tr (C. Erkey).

http://dx.doi.org/10.1016/j.jcou.2017.06.008
Received 22 September 2016; Received in revised form 24 October 2016; Accepted 16 June 2017
Available online 09 August 2017
2212-9820/ © 2017 Elsevier Ltd. All rights reserved.
M. Anas et al.
Table 1
Summary of Studies on Carbon Dioxide Adsorption on Aerogels.
Aerogel Feed Composition
Amino-functionalized silica aerogel (5.2 wt% N) 100% CO2
Amine-modified silica aerogel 10% CO2, 10% H2O in N2
Carbon aerogel (from melamine-formaldehyde resin) 100% CO2
Carbon aerogel (from chitosan and polybenzoxazine) 100% CO2
100% CO2
100% CO2
Amine-hybrid silica aerogel 1% CO2 in N2
80 wt% Tetraetylenepentamine loaded silica aerogel 100% CO2
Silica aerogel 100% CO2
Chitosan-(20%) graphene oxide aerogel 100% CO2
different native and modified aerogels have also been reported. Some
studies reported adsorption capacity at a single temperature and pres-
sure [15,19] while others determined adsorption isotherms showing the
relationship between the amounts of CO2 adsorbed and pressures at a
constant temperature [20,21]. Adsorption isotherms are necessary not
only for design and modeling of adsorption systems but also for eval-
uating properties such as heats of adsorption [22]. Silica aerogel and
amine-modified silica aerogels had CO2 adsorption capacities in the
range of 3.30–6.97 mmol g−1 at 298 K and 1 bar [18,23–25]. Similarly,
carbon aerogels synthesized from different organic precursors had CO2
adsorption capacities in the range of 2.20–6.70 mmol g−1 at 298 K and
1 bar [19,21,26]. Table 1 provides a summary of studies on aerogels
along with their maximum CO2 adsorption capacity. There is no sys-
tematic study in the literature on the effect of pore properties such as
pore size, pore volume, and surface area of different aerogels on CO2
adsorption. There are also no studies on organic aerogels and CO2 ad-
sorption on aerogels at high pressures.
In this study, silica aerogel, two resorcinol-formaldehyde aerogels
with different pore sizes, carbon aerogel, and wheat starch aerogel were
synthesized and excess adsorption isotherms of CO2 on these aerogels
were measured at 308 K, 318 K, and 328 K and at pressures up to 35 bar
using a volumetric method. The absolute (total) adsorption isotherms
were also calculated from excess adsorption isotherms. Isotherms were
fitted with Langmuir and Freundlich models and isosteric heats of ad-
sorption were also calculated.
2. Experimental
2.1. Materials and Synthesis of Aerogels
Resorcinol (99%), sodium carbonate (99.99%), and ethanol (99.9%)
were purchased from Merck. Formaldehyde (36%) was purchased from
Lachema. Tetraethylorthosilicate (TEOS) (98.0%) and ammonium hy-
droxide (2.0 M in ethanol) were purchased from Sigma Aldrich, and
hydrochloric acid (37%) was purchased from Riedel-de Haen. Wheat
Starch was purchased from Kenton (Turkey). Chemicals were used as-
received. Water was distilled and deionized. Carbon dioxide (99.998%),
nitrogen (99.99%), and helium (99.999%) were purchased from Air
Liquide.
2.1.1. Silica Aerogel
Tetraethylorthosilicate, distilled water, and ethanol were mixed in
the presence of acid catalyst (HCl in ethanol) for 30 min. Then base
catalyst, ammonia solution in ethanol, was added and the mixture was
stirred for 1 minute. The molar ratios of the chemicals,
TEOS:ethanol:H2O:HCl:NH4OH were 1:1.01:2.97:0.0022:0.0089.
Solution was then transferred into a mold and left for 30–40 minutes
until gel was formed. Gel was then put into a solution (50% water and
50% ethanol) and placed in the oven at 50 °C for 24 hours. Solvent
exchange with pure ethanol was then carried out to obtain alcogel.
Alcogel was dried using supercritical CO2 for extraction of the solvent
83
Journal of CO₂ Utilization 21 (2017) 82–88
Temperature (K) Pressure (bar) Maximum Capacity (mmol g−1) Reference
298 0.025 0.523 [15]
298 1 6.97 [18]
298 1 2.2 [19]
298 1 5.72 [21]
273 1 6.70
298 2 6.25
298 1 5.55 [23]
348 1 6.10 [24]
298 1 3.3 [25]
298 1 4.15 [26]
in the Applied Separations SFE unit which consists of a high pressure
extraction vessel (500 mL) in an oven, a pump, a carbon dioxide cy-
linder, a cooler, a rotameter and a control unit for controlling the
temperature of the extractor and the expansion valve. Drying was
performed at 40 °C and 100 bar with a CO2 flow rate of 1.5 L/min for
8 hours. After the extraction was over, the vessel was slowly de-
pressurized at 40 °C and aerogels were obtained.
2.1.2. Resorcinol-Formaldehyde Aerogel
Resorcinol-formaldehyde aerogels (RFAs) were synthesized based
on the procedure described by Pekala [27]. Two different types of RFAs
were synthesized based on their pore sizes. One had a pore size of
19 nm and another had a pore size of 7 nm. For the preparation of
RFAs, resorcinol was first dissolved in water and alkaline catalyst so-
dium carbonate was then added to the solution. Resulting mixture was
stirred for 10 minutes and then formaldehyde was added. For the RFA
with pore size of 19 nm (RFA-19), resorcinol to formaldehyde ratio of
0.5, resorcinol to alkali catalyst ratio of 200, and resorcinol to water
ratio of 0.02 was used. For the RFA with pore size of 7 nm (RFA-7),
resorcinol to formaldehyde ratio of 0.5, resorcinol to alkali catalyst
ratio of 50, and resorcinol to water ratio of 0.08 was used. The mixture
was then poured into a sealed container. The solutions were cured at
room temperature for 24 hours, for another 24 hours at 50 °C, and for
72 hours at 90 °C. Resulting gels were taken out of their molds and
placed in acetone. Solvent exchange with pure acetone was carried out
to obtain acetogels. Acetogels were dried using supercritical CO2 for
extraction of the solvent at 50 °C and 138 bar with a CO2 flow rate of
1.5 L/min for 8 hours. After the extraction was over, the vessel was
slowly depressurized at 50 °C and aerogels were obtained.
2.1.3. Carbon Aerogel
Carbon aerogel was prepared via pyrolysis (carbonization) of RFA-
19 at 1000 °C in flowing N2 (100 ml min−1) for 6 hours.
2.1.4. Wheat Starch Aerogel
Wheat starch aerogel was synthesized according to the method de-
scribed by De Marco et al. [28]. A homogenous starch solution with
5 wt% wheat starch was prepared in distilled water and then gelati-
nized at 110 °C. The hydrogel was poured into molds and placed in the
fridge for retrogradation at 4 °C for 72 hours. Alcogel was obtained by
replacing water in the pores with ethanol at room temperature. In-
creasing ethanol concentration (30%, 50%, 70%, 90% and two times
100% v/v) were used for solvent exchange and each exchange lasted for
24 hours. Alcogels were then dried using supercritical CO2 for extrac-
tion of the solvent at 40 °C and 100 bar with a CO2 flow rate of 1.5 L/
min for 8 hours. After the extraction was over, the vessel was slowly
depressurized at 40 °C and aerogels were collected.
2.2. Material Characterization and CO2 Adsorption Measurements
The Brunauer-Emmett-Teller (BET) surface area (SA), pore size, and
M. Anas et al. Journal of CO₂ Utilization 21 (2017) 82–88

pore volume of aerogels were obtained by 60-point N2 adsorption-

desorption isotherms at 77 K with a Micrometrics ASAP 2020 instru-
ment. Samples were degassed for 24 hours under vacuum at 300 °C for
silica aerogel and 80 °C for carbon, resorcinol-formaldehyde, and wheat
starch aerogels. Pore size distributions were derived from the in-
corporated software of the instrument using the Barrett-Joyner-Halenda
(BJH) method. CO2 adsorption isotherms were obtained using a High
Pressure Volumetric Analyzer (HPVA-II Micrometrics) which employs a
static volumetric technique and uses pure CO2 (99.998%) for adsorp-
tion and pure helium for free space measurement. Prior to CO2 ad-
sorption measurements, samples were degassed for 24 hours under
vacuum at 300 °C for silica aerogel and 80 °C for carbon, resorcinol-
formaldehyde, and wheat starch aerogels in the degas chamber. After
degassing the samples, sample holder was attached to the analysis port
and the system was purged with helium gas followed by free space
measurement and adsorption measurement using CO2 allowing equili-
bration time of 45 to 60 minutes. Fig. 1. Pore Size Distribution of Aerogels.

3. Results and Discussion

3.1. Surface Area and Pore Size Distribution

N2 adsorption-desorption isotherms were used to determine the

surface area and pore properties of aerogels which are summarized in
Table 2. Pore volumes of the aerogels ranged from 0.57 cm3 g−1 to
5.5 cm3 g−1 and surface areas ranged from 128 m2 g−1 to 1158 m2 g−1.
Pore size distribution curves (PSD) were also obtained using BJH
analysis for all aerogels and are shown in Fig. 1. According to the
IUPAC classification, porous materials are classified according to their
pore sizes which are microporous (Dp < 2 nm), mesoporous (Dp be-
tween 2 nm and 50 nm), and macroporous (Dp > 50 nm) [29]. As
shown in Fig. 1, all aerogels synthesized show sharp distributions with a
maxima of 15 nm for silica aerogel, 5 nm and 15 nm for two different
resorcinol-formaldehyde aerogels, 15 nm for carbon aerogel, and
14.5 nm for wheat starch aerogel. All distributions primarily lie in the
Fig. 2. Excess Adsorption Isotherms of CO2 at 308 K.
mesoporous region indicating dominance of mesopores in aerogels.

3.2. Excess CO2 Adsorption and Surface Area

Fig. 2 shows the excess adsorption isotherms for CO2 on various

aerogels at 308 K and at pressures up to 35 bar. Silica, resorcinol-for-
maldehyde, and carbon aerogels show increase in uptake with increase
in pressure while wheat starch aerogel show increase up to a certain
pressure before reaching an asymptotic value. Similar trends were also
observed at 318 K and 328 K. Uptake at each pressure was found to be
proportional to the mesopore surface area of aerogels which was cal-
culated by subtracting micropore surface area from BET surface area.
Fig. 3 shows the relationship between uptake and mesopore surface
areas of aerogels at 308 K and at pressures of 1 bar, 10 bar and 30 bar.
At 1 bar, CO2 uptake increases with surface area of aerogels except for
silica aerogel which despite having the highest mesopore surface area
of 1158 m2 g−1 has adsorption capacity lower than that of carbon
aerogel (Mesopore SA = 558 m2 g−1), RFA-7 (Mesopore Fig. 3. The Variation of Excess Uptake with Mesopore Surface Area of Aerogels at 308 K.
SA = 806 m g ), and RFA-19 (Mesopore SA = 524 m2 g−1). This is
2 −1

due to the lower affinity of CO2 to the silica aerogel surface at low

Table 2
Surface Area and Pore Properties of Aerogels.

Aerogel BJH Pore Volume, Vp (cm3 g−1) Average Pore Diameter, Dp (nm) BET Surface Area, SBET (m2 g−1) Micropore Surface Area (m2 g−1)

Silica 4.6 15 1158 –

Resorcinol-Formaldehyde (RFA-19) 5.5 19 620 96
Resorcinol-Formaldehyde (RFA-7) 1.5 7 855 49
Carbon 3.7 16 900 342
Wheat Starch 0.57 18 128 16

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M. Anas et al. Journal of CO₂ Utilization 21 (2017) 82–88

pressures [16]. At pressures of 10 bar and 30 bar, CO2 uptake increases

with mesopore surface area. This relationship is also confirmed by
noting that carbon aerogel (SBET = 900 m2 g−1) and RFA-19
(SBET = 620 m2 g−1) have similar uptakes because of similar mesopore
surface areas even though there is a significant difference between the
BET surface area of two aerogels.

3.3. Absolute Adsorption Isotherms

Development of adsorption systems for CO2 at especially high

pressures requires absolute or total amount adsorbed to be known and
the adsorbed amount obtained in experiments is the Gibb’s surface
excess (Γexcess) [30]. For a flat surface, Γexcess is defined by Eq. (1) which
is given by:
∞
Γexcess = ∫ [ρ(z) − ρ bulk ]dz
0 (1) Fig. 5. Adsorption Isotherms for RFA-19.

where ρ is the density of the adsorbate and z is the distance from the
solid surface. The absolute adsorption is given by:
Γabsolute = Γexcess + ρfluid (Vpore − Vads) (2)
−1
where Γabsolute is absolute adsorbed amount in mmol g , Γexcess is ex-
cess adsorbed amount in mmol g−1, ρfluid is molar density of the fluid in
mmol cm−3, Vpore is volume of the pore in cm3 g−1, Vads is volume
adsorbed in cm3 g−1. The first term in the right hand side of Eq. (2) is
the excess amount adsorbed obtained experimentally and second term
is the amount of the bulk fluid that is inside the pores but not adsorbed
on the surface of the pores. Volume adsorbed is calculated by using Eq.
(3) and density of the adsorbed phase, ρads, is assumed to be the inverse
of van der Waal’s constant for carbon dioxide [31,32].
Γexcess
Vads =
ρads (3)

Absolute adsorption isotherms were calculated from excess ad-

sorption isotherms using Eqs. (2) and (3). The molar density of CO2 at Fig. 6. Adsorption Isotherms for RFA-7.
each temperature and pressure was taken from NIST Chemistry Web-
book [33]. Figs. 4–8 show excess and absolute adsorption isotherms at
308 K, 318 K, and 328 K for silica aerogel, RFA-19, RFA-7, carbon
aerogel, and wheat starch aerogel respectively.
All isotherms can be classified as type I and both absolute and excess
uptake at each pressure decreases with increase in temperature for all
aerogels which indicates that the adsorption is physical and exothermic
[2,21,34]. Since the difference between the absolute and excess ad-
sorbed amount is dependent on the pore volume of the adsorbent, it is
found that there is a significant difference between two quantities at all
pressures. For silica aerogel, the difference is 34% at 1 bar and is more

Fig. 7. Adsorption Isotherms for Carbon Aerogel.

Fig. 4. Adsorption Isotherms for Silica Aerogel.
than 74% at pressures greater than 20 bar. Similarly, for RFA-19, the
difference is 30% at 1 bar and is more than 130% at pressures greater
than 20 bar. The difference for carbon aerogel is 20% at 1 bar and is
more than 95% at pressures greater than 20 bar. For RFA-9, the dif-
ference is 7% at 1 bar and is more than 24% at pressures greater than
20 bar. Finally, the difference for wheat starch aerogel is 8% at 1 bar
and is more than 34% at pressures greater than 20 bar. The differences
among aerogels are due to the differences in pore volumes of aerogels
which were given in Table 2. Silica aerogel, RFA-19, and carbon aerogel

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M. Anas et al. Journal of CO₂ Utilization 21 (2017) 82–88

3.4. Adsorption Isotherm Models

Langmuir and Freundlich isotherm models are the most commonly

used models for correlating CO2 adsorption isotherms [21,26]. The
Langmuir isotherm is given by:
Kqm P
q=
1+KP (4)

where q is the amount adsorbed at pressure P and K and qm are Lang-

muir isotherm parameters. The Freundlich isotherm is given by:

q= Kf P1/n (5)

where q is the amount adsorbed at pressure P, Kf is the Freundlich

Fig. 8. Adsorption Isotherms for Wheat Starch Aerogel.
have high pore volumes which result in larger difference between total
and excess adsorbed amounts. RFA-7 and wheat starch aerogel have
low pore volumes which lead to smaller differences between the total
and excess adsorbed amounts. Moreover, for aerogels excess adsorbed
and absolute adsorbed amounts are not nearly equal at low pressures
which is generally the case for conventional adsorbents [30]. For ex-
ample, excess and absolute adsorbed amounts for activated carbon with
a BET surface area of 850 m2 g−1 and pore volume of 0.66 cm3 g−1
were nearly equal up to pressures of almost 25 bar [32].
It would also be interesting to compare excess uptakes for carbon
aerogels to other carbonaceous adsorbents. An excess adsorbed amount
of about 0.008 mmol m−2 at 25 bar and 36 °C was reported for acti-
vated carbon while carbon aerogel in this study had excess uptake of
0.004 mmol m−2 at 25 bar and 35 °C [32]. The lower value for carbon
aerogel suggests that the surface of carbon aerogel has less affinity for
CO2. However, absolute uptakes are similar due to the higher pore
volume (3.7 cm3 g−1) of aerogel than activated carbon (0.66 cm3 g−1).
It is, therefore, recommended that excess isotherms should be corrected
at all pressures for reliable and accurate design and modeling of ad-
sorption systems involving aerogels.
The results also indicate that some of the aerogels investigated in
this study have significantly high absolute CO2 adsorption capacities at
high pressures. For instance, silica aerogel has a maximum absolute
adsorption uptake of 14 mmol g−1 and RFA-19 has a maximum uptake
of 13 mmol g−1 at 308 K and 35 bar, which are comparable with ad-
sorption capacities of other adsorbents such as zeolites and activated
carbon at high pressures [16,17]. These results suggest that modified
aerogels with high excess adsorption capacity at ambient conditions
such as amine-modified silica aerogel prepared by Cui et al. [18] and
carbon aerogel synthesized from chitosan-polybenzoxazine nano-
composites by Alhwaige et al. [21] may have really high absolute ad-
sorption capacities at high pressures.
proportionality constant, and n is the heterogeneity parameter.
Nonlinear regression was performed on the absolute adsorption data
to determine the isotherm parameters. The goodness of fit of the model
was evaluated by the correlation parameter R2. Langmuir model pro-
vided a good fit for silica, resorcinol-formaldehyde, and wheat starch
aerogels indicating a homogenous surface in these aerogels while
Freundlich model provided a good fit for carbon aerogel indicating an
energetically heterogeneous surface of the aerogel which is also con-
firmed by the large number of micropores in the carbon aerogel [26].
Isotherm parameters at all temperatures are summarized in Table 3.
3.5. Isosteric Heats of Adsorption of Aerogels
Carbon dioxide excess adsorption isotherms at 308 K, 318 K, and
328 K for all aerogels were used to calculate isosteric heat of adsorp-
tion, Qst, which is an important thermodynamic parameter because it
represents the strength of adsorbent-adsorbate interaction [35]. To
calculate isosteric heat of adsorption, value of pressure, P, is de-
termined at different temperatures, T, from CO2 adsorption isotherm for
a constant equilibrium excess uptake and the slope is determined from
the plot of lnP against 1/T as given by the Clausius-Clapeyron equation
[30,32,35]:
∂lnP Qst
=
∂ ()
1
T n
R
(9)
where R is the molar gas constant.
Since heat of adsorption is dependent on the excess uptake [20], Qst
values were determined at different excess uptake amounts. There was
no significant difference in Qst values and the maximum variation be-
tween the highest and lowest values did not exceed 5%. Therefore, an
average Qst was calculated. Table 4 lists the average isosteric heat of
adsorption for all aerogels investigated. Negative values show that the
adsorption is exothermic and the higher the value of Qst, the stronger is
the interaction of CO2 with the aerogel. The highest value for wheat
starch aerogel among all the aerogels investigated in this study in-
dicates the strongest interaction of CO2 molecules with surface active
sites, however, the uptake is low due to the low surface area of the
wheat aerogel. The lowest value for carbon aerogel is indicative of weak
interaction of CO2 with surface active sites and is comparable with the

Table 3
Langmuir and Freundlich Parameters.

Temperature (K) 308 318 328

−1 −1 −1 −1
Langmuir Parameters K (bar ) qm (mmol g ) R2
K (bar ) qm (mmol g ) R2
K (bar−1) qm (mmol g−1) R2
Silica Aerogel 0.01110 49.98 0.9988 0.01076 45.77 0.9992 0.009622 45.01 0.9995
RFA-19 0.01326 40.05 0.9939 0.01211 40.05 0.9949 0.01176 37.66 0.9965
RFA-7 0.03993 13.78 0.9879 0.03904 12.66 0.9897 0.04000 11.35 0.9926
Wheat Starch Aerogel 0.06939 3.021 0.9872 0.07758 2.373 0.9910 0.07220 2.216 0.9948
Freundlich Parameters Kf n R2 Kf n R2 Kf n R2
Carbon Aerogel 0.7134 1.329 0.9946 0.6832 1.341 0.9959 0.6356 1.338 0.9969

86
M. Anas et al.
Table 4
Isosteric Heat of Adsorption for Aerogels.
Aerogel Qst(kJ mol−1)
Silica −21.9
RFA-19 −21.8
RFA-7 −18.4
Carbon −17.7
Wheat Starch −32.1
value of −19.23 kJ mol−1 reported for activated carbon [36] and the
value of −17.2 kJ mol−1 reported for the carbon aerogel synthesized
from chitosan-polybenzoxazine nanocomposite [21]. The heat of ad-
sorption of silica aerogel is similar to the value of −22 kJ mol−1 re-
ported for mesoporous silica, MCM-41 [37]. Low values of isosteric heat
of adsorption for aerogels are also indicative of low energy requirement
for their regeneration which is an important consideration in selection
of an adsorbent.
4. Conclusions
Silica, resorcinol-formaldehyde, carbon, and wheat starch aerogels
were synthesized in this study and excess CO2 adsorption isotherms
were measured to gain insight into these aerogels’ potential as ad-
sorbents for carbon capture. Total or absolute adsorption isotherms
were calculated from experimentally obtained excess adsorption by
taking into account the amount of bulk fluid in the pores which is not
adsorbed. The total amount adsorbed was found to differ from excess
amount significantly especially at high pressures due to large pore vo-
lumes of aerogels which is important for the design of adsorption sys-
tems based on aerogels. Silica aerogel (SBET=1158 m2 g−1) had a
maximum absolute CO2 adsorption uptake of 14 mmol g−1 and RFA-19
(SBET=620 m2 g−1) had a maximum uptake of 13 mmol g−1 at 308 K
and 35 bar. It was also found that the excess CO2 uptake was propor-
tional to the mesopore surface area of aerogels at various pressures.
Isosteric heats of adsorption for all aerogels were also determined to
investigate adsorbent-adsorbate interaction strength and wheat starch
aerogel had the highest value of −32.1 kJ mol−1 followed by silica,
resorcinol-formaldehyde and carbon aerogels. Results presented in this
study demonstrate the need to further investigate native and modified
aerogels as potential carbon capture materials especially at high pres-
sures. Aerogels may provide a solution to the persisting problem of
capturing CO2 for sequestration as well as separating CO2 from sour
natural gas reserves.
Acknowledgements
The authors are grateful for the support of Koç University Tüpraş
Energy Center (KUTEM) at Koç University and Arcelik.
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M. Anas et al.
Muhammad Anas received his B.S. degree from Texas
A & M University at Qatar in 2014. Currently, he is a Master
of Science student in the Chemical and Biological
Department at Koç University.
Abdullah Göktuğ Gönel received his B.S. and M.S. degrees
in Chemical and Biological Engineering from Koc
University in 2014 and 2016. He is currently a Ph.D. stu-
dent in the Chemical Engineering Department at University
of California Davis, USA.
88
Journal of CO₂ Utilization 21 (2017) 82–88
Selmi Erim Bozbag is currently a postdoctoral research
associate in the Chemical and Biological Engineering
Department at Koç University working on the development
of catalytic after-treatment systems for diesel engines.
During his Ph.D., he worked on the preparation of aerogel
supported bimetallic nanoparticles using supercritical
fluids. His research focuses on the fundamental aspects of
heterogeneous catalysis, adsorption, nanostructured mate-
rials and supercritical fluids.
Can Erkey received his B.S. degree in Chemical
Engineering from Boğaziçi University in Istanbul, Turkey in
1984 and Ph.D. degree in Chemical Engineering from Texas
A & M University, College Station, USA in 1989. He served
as an Assistant Professor, Associate Professor and Professor
in the Department of Chemical Engineering at the
University of Connecticut. He has been a professor in the
Chemical and Biological Department at Koc University in
Istanbul, Turkey since 2006. He is serving as the director of
the Koc University Tüpraş Energy Center (KUTEM). His
research interests are in nanostructured materials, energy
and supercritical fluids.