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Ionic liquid containing amine-based silica aerogels for CO2


capture by fixed bed adsorption

Müjde Garip, Nilay Gizli

PII: S0167-7322(20)30444-X
DOI: https://doi.org/10.1016/j.molliq.2020.113227
Reference: MOLLIQ 113227

To appear in: Journal of Molecular Liquids

Received date: 21 January 2020


Revised date: 21 March 2020
Accepted date: 23 April 2020

Please cite this article as: M. Garip and N. Gizli, Ionic liquid containing amine-based silica
aerogels for CO2 capture by fixed bed adsorption, Journal of Molecular Liquids (2018),
https://doi.org/10.1016/j.molliq.2020.113227

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© 2018 Published by Elsevier.


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Ionic Liquid Containing Amine-Based Silica Aerogels for CO2 Capture by


Fixed Bed Adsorption

Müjde Garipa, Nilay GİZLİb*


a
Ege University, Graduate School of Natural and Applied Science,Material Science and Engineering
Programme İzmir/Turkey
b
Ege University, Chemical Engineering Department, İzmir/Turkey

ABSTRACT

The main goal of this study is to develop an adsorption based process using amine-based silica

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aerogels to capture CO2 from post-combustion gases. For this purpose, silica based aerogels were

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synthesized by following single-step sol-gel method using tetraethyl orthosilicate (TEOS) as silica
precursor and (3-Aminopropyl)triethoxysilane (APTES) as amine source in different compositions.
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To enhance CO2 capture performances of the prepared aerogels, amine-containing ionic liquid (1-
Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) was also used as sol agent due to high
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CO2 selectivity and lower viscosity. Chemical structural properties, thermal behaviors, surface area
and morphologies of prepared aerogels were analyzed. CO2 capture performances of prepared
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aerogels were investigated in a fixed bed column of CO2 capture experimental set-up for adsorption.
Results have shown that CO2 adsorption capacities of ionic liquid containing amine-based aerogels
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increased with the addition of amine source and ionic liquid. Among the prepared aerogels, the
sample of TA0.24IL0.28 exhibited superior adsorption behavior with the maximum capacity of 243.32
mg CO2/g (5.53 mmol/g).
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Keywords: CO2 capture, ionic liquid, aerogel, silica, adsorption


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INTRODUCTION

Global emissions of CO2 involve a constant increase at an accelerating rate resulting in the
concentration of atmospheric CO2 to reach 407 ppm in 2018 compared to 280 ppm in preindustrial
time [1]. In the special report by “Intergovernmental Panel on Climate Change” (IPCC), this
excessive CO2 emission is considered as the major source of the greenhouse gases that causes various
environmental problems due to the global warming and climate change [2]. Hence, there is a crucial
need to develop new strategies to reduce the anthropogenic CO2 emissions. Currently, CO2 capture
and storage (CCS) is regarded as an important technology for mitigation of CO2 emissions from fossil
fuel sources into the atmosphere [3–5]. Most of CCS technologies include sorption-based processes

*Corresponding author.
E-mail address: nilay.gizli@ege.edu.tr (N. Gizli)
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such as physical and chemical absorption and solid-state adsorption [6]. Amine-based solutions have
been commercially utilized due to their reversible chemical reactions between alkanolamines and
CO2, high CO2 capturing selectivity and capability of capturing CO2 from several gas streams at low
CO2 partial pressures [7–9]. However, there are some strict obstacles such as: high enthalpy of
reaction, low absorption capacity, high energy consumption of liquid solvent regeneration, oxidative
and thermal degradation and equipment corrosion [10,11]. Moreover, through capturing CO2 from
air, there will be a significant solvent loss via evaporation since the solvent needs to be in contact with
a massive amount of air. This situation leads to more chemical requirement and also additional cost
[12]. To avoid aforementioned drawbacks and to overcome the limitations of absorption processes
using amine-based solutions, the development of solid sorbents has received much attention [12,13].
A variety of porous solid sorbents such as mesoporous silica [14,15], aerogel [16], zeolite [9,17],

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metal organic framework [18–22] activated carbon [18], mesoporous alumina [23] metal oxides [24]
and covalent organic polymers [25–28] have been currently under investigation for these purposes.

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Although these porous materials possess high surface area, high pore volume, and large pore size,
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they originally have limited adsorption capacity and low selectivity for CO2 in the presence of the
other gases such as N2 [29,30]. In order to improve the CO2 adsorption capacity further, amine species
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can be incorporated into the porous support by following physical impregnation, chemical grafting or
direct (one–pot) synthesis methods [13, 31,32]. By this means, physical adsorption of CO2 is
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promoted by the chemical adsorption through the reaction of amine species with CO2 forming
carbamates. Among the various support materials for amine incorporation, silica aerogels have drawn
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widespread interest because of their superior properties of high surface area, high pore volume and
low density [32]. Lineen and co-workers prepared an amine functionalized silica aerogel by physical
impregnation of tetraethylenepentamine (TEPA) [33]. They determined CO2 adsorption performances
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by using electromicrobalance as about 6 mmol/g. In their second paper, Linneen et al., developed a
particulate silica aerogels by functionalizing them with mono, di and tri-amine covalently and
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evaluated their capacities using CO2 gravimetric adsorption analysis as 1.76 mmol/g and 2.61 mmol/g
for dry and wet grafting, respectively [33]. Kong et al., conducted various studies including synthesis
of amine hybrid aerogels and investigation of CO2 capture performances in a fixed bed column.
Firstly, they prepared amine hybrid resorcinol-formaldehyde/silsesquioxane composite aerogel (AH-
RFSA) using APTES as an amine source through polymeric sol-gel process and Supercritical Drying
(SCD) method [16]. Then, they synthesized an amine hybrid silsesquioxane aerogel (AHSA) using
Tetraethoxysilane (TEOS) as silica precursor and APTES as an amine source through a single-step
sol-gel method followed by SCD [34]. After that, they extended their studies by preparing amine
hybrid zirconia/silica aerogels (AHZSA) using APTES via one-pot sol-gel synthesis [35]. Lastly, they
conducted their studies by preparing a new amine hybrid titania/silsesquioxane composite aerogel
(AHTSA) using APTES via one-pot sol-gel process. They concluded that the dominant factor for the
CO2 adsorption capacity might be surface amine content instead of the amine loading on the matrix
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[36]. Cui et al, prepared mesoporous amine based SiO2 aerogels (AMSA) having the CO2 sorption
capacity of 6.97 mmol/g in the presence of water. using sol-gel methods and supercritical drying [37].

On the other hand, ionic liquids (ILs) have drawn great attention due to their unique properties such as
negligible volatility, high thermal and chemical stability, tunable physicochemical properties for the
CO2 capture processes as an alternative to traditional amine-based sorption processes. [38–46]. IL can
be applied to absorb CO2 by either physical or chemical absorption. There are many screening studies
in the literature on the CO2 solubility of the ionic liquids using solubility measurements,
spectroscopic and/or molecular dynamic simulations. It is generally concluded that anion part of the
ionic liquids plays dominant role in the solubility of CO2. The ionic liquid with Tf2N anion has a
considerably higher affinity due to the favourable interactions between CO2 and fluoroalkyl

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substituents on the anion [39,47,48]. Bearing this in mind, ethyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide (EMIMTf2N) is selected as an ionic liquid in the present study.

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However there exists a mass transfer limitations in consequence of the high viscosity possessed by ILs
[49,50]. Incorporation of IL into a porous support is proposed as a potential adsorbent to mitigate
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these drawbacks. Moreover, IL confinement within porous support can contribute additional benefits
by combining the advantages of high CO2 sorption capacity of ILs with high surface area of porous
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materials. Thus the usage of ILs with porous support material, namely supported ionic liquid phase
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(SILP) has become the main topic of the relevant researches [51–56]. As in most of the studies
conducted, SILPs are prepared by physical impregnation method based on the electrostatic interaction
between functional group of the selected IL and solid support for CO2 capture [57–60]. Although,
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SILP preparation by physical impregnation is an uncomplicated method in providing high IL content;


their vulnerable performances in the sorption processes due to the leakage of the ILs is still a worth-
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stressing issue. To overcome this restraint, ionic liquids should be incorporated to solid structure
directly during the synthesis of 3D network. Although numerous researches have focused on in-situ
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application of IL into sol-gel silica formation, they either were related to the structural control and
morphological alteration of the silica network [61–67] or improving the efficiency and the selectivity
of the porous materials for the adsorption applications (i.e, CO2 capture) [68]. Yet still, none of these
reports has deal with the direct usage of amine containing precursors along with the ionic liquids in
the one-pot synthesis of the silica aerogels for the capture of CO2 .

In the present study, it is aimed to produce silica aerogel adsorbent for CO2 capture, via one-pot sol-
gel process using 3-aminopropyltriethoxysilane (APTES) co-precursor in the presence of imidazolium
based ionic liquid, ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIMTf2N), for
the first time. In this way, the CO2 sorption performance of the prepared materials will be promoted
by combining the three main effects: 1) the favourable affinity of fluoroalkyl groups of (EMIMTf2N)
in CO2 solubility [47] 2) the chemisorptions through the interaction between amine species of APTES
and CO2 by means of zwitterions mechanism to form carbamates as described by Caplow [69–71] and
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3)Physisorption due to the highly porous characteristics of prepared aerogel. CO2 sorption
performances of the prepared adsorbent containing diverse amount of amine species (APTES) and IL
were examined by a series of fixed bed column mode adsorption studies.

EXPERIMENTAL PROCEDURE
2.1. Materials

Tetraethyl ortosilicate (TEOS, 98%) used as a silica precursor and 3-aminopropyltriethoxysilane


(APTES) used both as an amine source along with as a co-precursor were supplied from Sigma
Aldrich. 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIMTf2N), (IL, 98%,

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CAS Number: 174899-82-2) was purchased from Sigma Aldrich. The chemical structures of silica
precursors and ionic liquid are presented in Figure 1. During the sol-gel process, to ensure hydrolysis,

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ethanol (EtOH) was used in the aqueous media (deionized water) and hydrochloric acid (HCl) was
involved as catalyst.
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TEOS APTES EMIM TF2N


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Figure 1 Chemical structures of sol precursors and ionic liquid.


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2.2. Methods

Amine hybrid silica aerogels were prepared by one step sol-gel process as illustrated in Figure 2.
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Figure 2 Amine hybrid silica aerogel preparation steps with the corresponding reactions.
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During the sol preparation, the mixture of TEOS and EMIM(Tf2N) were hydrolyzed by using HCl in
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EtOH and deionized H2O media for 90 minutes under vigorous stirring. The gelation becomes distinct
with the addition of APTES. The amount of EMIM(Tf2N) and APTES were diversed within the sol
while keeping the mole ratios of TEOS:EtOH:H2O as 1:3.5:2. The final mixture was then exposed to
an aging period in a mold for day along to accomplish the condensation reaction. Afterwards, the
alcolgels were let to stay in vacuum oven to ensure complete drying under ambient conditions for 24
hours. Finally, the aerogels were grinded to obtain samples in granular form.

Through the following one-step sol-gel process, a variety of amine hybrid silica aerogels were
prepared by changing the amount of EMIM(Tf2N) and APTES. The resultant materials were
abbreviated as TAxILy. where T, A and IL represented TEOS, APTES and EMIM(Tf2N)(ionic
liquid); the subscript of x and y referred the mol ratios of APTES and IL, respectively. Herein, x and y
ratios were varied as 0.24, 0.50, 0.74 and 0.06, 0.15, 0.18, 0.28, respectively.
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2.3. Characterization

Fourier Transform Infrared Spectroscopy (FT-IR, Spectrum 100 Perkin-Elmer) were performed
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within the wave number range of 500-4000 cm in order to identify the significant chemical bonds.
Morphological structures of the prepared aerogels were examined by Scanning Electron Microscopy
(SEM, Thermo Scientific, Apreo S) at the acceleration voltage of 20 kV with 10000 magnification
rate. Thermo gravimetric analysis (TGA) were also implemented by using TA Instruments Q20 to
reveal the thermal behaviors of aerogel samples with a heating rate of 5 C/min. Surface area and pore
structure of prepared materials were characterized by physisorption of N2 using Micrometrics, 3 Flex
Physisorption .

2.4 CO2 capture studies by adsorption

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CO2 adsorption behaviors of the prepared aerogels were investigated by a series of column-mode

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adsorption studies at the ambient condition. The experimental set-up consists of a fixed bed column
having the diameter of 35 mm and length of 700 mm as shown in Figure 3. Inert quartz particles were
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packed in the top and bottom part of the column in order to satisfy the perfect mixing of individual
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gas streams and conditioning the column for dynamic operation. The samples were hold between
glass wool supports in the quartz bed. The mixture of CO2 and N2 were introduced into a column
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through upward direction with 30, 50, 70 % volume percent of CO2. Prior to CO2 adsorption, the
sorbents were degassed under a nitrogen flow of 50 mL min−1 at ambient condition for 30 min. The
CO2 gas concentrations of the exit stream with respect to time were detected by infrared gas analyzer
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containing data logger (Vernier LQ2-LE) in the operating range of 0-10000 ppm with the accuracy
rate of ± 0.1 ppm. Before each experiment, gas analyzer was calibrated in order to adjust the response
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on CO2 concentration values. During the calibration period, the flow of CO2/N2 gas mixture is
directed to gas analyzer by a by-pass line. The breakthrough adsorption capacities were obtained by
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the change in CO2 concentration of the exit stream depending on time by using the following relation.

∫ (1)

Where is the specific CO2 adsorption capacity as mg/g. is the amount of adsorbent packed
into the column (g), refers to the volumetric flowrate of the total gas stream at the inlet of the
column as ml/min. and are the concentrations of CO2 at the inlet and the exit of the
column recorded as mg/L.

Breakthrough point for the operation was selected as 400 ppm which is the average CO2 concentration
of the atmosphere. Column mode experiments were repeated at least three times to achieve consistent
results.
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Figure 3 Schematic diagram of CO2 capture set-up: 1) CO2 tube; 2) N2 tube; 3) Flow meters; 4)
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Manometer; 5) Three-way valve; 6) Sorbent bed; 7) Glass wool support 8) Quartz bed 9) Gas analyser
with data logger.
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RESULTS AND DISCUSSION

3.1. Characterization of prepared adsorbents


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The FT-IR spectra of the synthesized silica aerogels containing various amount of ionic liquid (Figure
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4) showed several bands of corresponding structural units. These spectrums revealed the symmetric
stretching vibrations of Si-O-Si appearing at 743-790 cm-1 and the asymmetric stretching vibrations of
Si-O-Si at the wavelength of 1032 cm-1 which is the indication for the formation of solid network.
Furthermore, the peaks which were observed at around 1349 cm-1 can be attributed to the presence of
the imidazolium ring of ionic liquid used in the sol preparation. So it can be said that IL can be
incorporated into the structure of the silica aerogel. Furthermore, as the amount of the ionic liquid
increased, the depth of these peaks was also increased eventhough the aerogels were synthesized
under the same conditions. Also, the peaks appeared around 1568 cm-1 wavelength can be associated
with the aminopropyl groups of APTES.
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TA0.24IL0.06

TA0.24IL0.15

TA0.24IL0.18
Transmittance (%)

TA0.24IL0.28

1568

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1349 743

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1900 1700 1500 1300
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Wavenumber (cm-1)
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Figure 4 FT-IR spectra of ionic liquid containing amine-based silica aerogel samples
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SEM images of the samples TA0.24IL0.18 and TA0.24IL0.24 were presented in Figure 5 in order to
demonstrate the effect of ionic liquid addition on the morphological characteristics of the aerogels.
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SEM images supported that, as the ionic liquid content increased from 0.18 mol to 0.28 mol, pore
structures of the prepared aerogels become distinct and the presence of ionic liquid lead to
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mesoporous formation. This situation was also affirmed by relevant studies of us which are about the
formation of mesoporous structures of aerogels in the presence of ionic liquid [66,72]. As depicted in
Figure 5.a, ionic liquid containing amine based aerogels consist of small primary particles. Herein,
primary particles agglomerated with the further increase in ionic liquid content and formed secondary
major particles as presented in Figure 5.b. This type of morphological formation is termed as pearl
necklace-like mesoporous structure consisting large vacancies [73]
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Figure 5 SEM images of a) TA0.24IL0.18 b) TA0.24IL0.28

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The effect of APTES content on the microstructure of the prepared aerogels were examined by the
SEM images of the samples TA0.24IL0.28 andTA0.74IL0.28 in Figure 6. It is observed that, with the
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increasing content of APTES (from 0.24 mol to 0.74 mol ), silica aerogel structures become denser.
This may be due to the rapid gelation which is accelerated by the existence of APTES. As a
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consequence, surplus APTES content may prevent pore formation of prepared aerogels and
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condensation reactions may occur without hydrolysis.


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Figure 6 The effect of APTES content on microstructure of prepared aerogels a) TA0.24IL0.28 b)


TA0.74IL0.28

In order to investigate the ionic liquid and APTES effect on the surface area and pore characteristics,
Nitrogen adsorption desorption isotherms were obtained as presented in Figure 7. It can be revealed
from Figure 5 that both two aerogel samples exhibited type IV isotherm with H3 hysteresis loop
according to the IUPAC classification of adsorption isotherms (10). This multilayered adsorption
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pathway is generally followed by capillary condensation which takes place in mesopores [74]. These
aerogel samples have non-rigid aggregates of plate like particles owing to their mesoporous nature.
The sample of TA0.24IL0.18 (Figure 5.a) contains almost no micropores and possesses small uptakes in
low relative pressures. On the other hand, ionic liquid content demonstrated significant effect on the
characteristics of hysteresis loop. Higher ionic liquid containing aerogel sample did not exhibit
obvious capillary condensation in high relative pressures (Figure 5.b). Further, the sharp increase was
observed due to the formation of macropores. This phenomenon may be expressed as the increase in
ionic liquid content disrupts the homogeneity of the pores.

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Figure 7 N2 adsorption isotherms and pore size distributions of a) TA0.24IL0.18 and b) TA0.24IL0.28 c)
TA0.50IL0.28 d) TA0.74IL0.28

Surface area and average pore diameter of prepared amine hybrid silica aerogels were evaluated by
using The Brunauer Emmet and Teller (BET) method. As given in Table 1, an increase in ionic liquid
content leads to higher surface area (from 1.26 to 6.37 m2/g). This situation supported the SEM
results. On the other hand, increasing the amount of ionic liquid caused a significant decline in the
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pore diameter values. Hence, TA0.24IL0.28 has higher surface area value when compared with
TA0.24IL0.18 owing to its smaller pores on physical structure. Moreover, a drastic decrease in surface
area values from 6.37 to 3.40 m2/g was related with the increase in APTES content (from 0.24 mol to
0.50 mol). This outcome can be clarified by in higher APTES ratios, amine groups coincided with
each other and minimized the reachable amine groups on surface area of prepared aerogels.

Table 1 Physical properties of ionic liquid containing amine-based silica aerogels

BET External Adsorption Average


Sample ID
Surface Area (m2/g) Surface Area (m2/g) Pore Diameter (Å)
TA0.24IL0.18 1.26 1.672 127.81
TA0.24IL0.28 6.37 7.909 110.40

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TA0.50IL0.28 3.40 4.227 90.03

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TA0.74IL0.28 3.59 4.550 71.65
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To investigate the thermal stability of the amine hybrid silica aerogels of TA0.24IL0.18, TA0.24IL0.28,
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TA0.50IL0.28, TA0.74IL0.28, thermo-gravimetric analysis (TGA) were performed (Figure 8).
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Figure 8 TGA profiles of TA0.24IL0.18, TA0.24IL0.28, TA0.5IL0.28 and TA0.74IL0.28


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As depicted in Figure 8, all samples exhibited similar thermal characteristics and maintained their
thermal stabilities within the temperature range of 25 °C and 400 °C. However, the profiles showed a
less than 5% weight loss between the room temperature and 110°C that can be attributed to the
evaporation of the water or residual solvents. The effect of ionic liquid amount on the thermal stability
of the sample can be revealed by comparing the TGA profiles of samples TA0.24IL0.18 and TA0.24IL0.28
in which APTES content was kept constant as 0.24 mole ratio and ionic liquid contents were altered
from 0.18 to 0.28 mole ratio. Both two samples denoted superior thermal stabilities up to the
temperature of 400 °C with total weight loss of 12%. This situation may be explained by the strong
physicochemical properties of ionic liquids such as high degradation temperature resulted from the
low vapor pressure. However, the weight loss increased with the increase in the content of APTES as
can be observed from TGA profiles of samples TA0.24IL0.28 TA0.5IL0.28 and TA0.74IL0.28 which can be

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ascribed to the release and decomposition of aminopropyl group of APTES.

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3.2.
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CO2 Adsorption performances of prepared aerogels

CO2 sorption performances of the amine hybrid silica aerogels were examined by obtaining
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breakthrough curves related with the CO2 concentration at the exit of the column corresponding with
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time.

3.2.1. Effect of gas flow rate


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CO2 adsorption experiments of the aerogel abbreviated as TA0.24IL0.06 was performed by setting the
inlet CO2 concentration as 30, 50, 70 and 100 % of CO2+N2 mixture. As presented in Figure 9, the
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total adsorption capacities of the aerogels increased regularly with increasing in inlet CO2
concentration. It can be seen from Table 2 that, the increase in CO2 concentration at the inlet stream
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(especially from 70 to 100 percent) assures high adsorption capacity together with successful CO 2.
capturing behavior. Nevertheless, during the practical operation using the experimental set-up, there
exists some difficulties in setting and keeping the flowrate constant at the desired value of 70 and 100
percent, since those flowrate values are very close to the upper limit of the flowmeters. On the other
hand, these concentration percentages are not applicable for simulating post-combustion gases.
Therefore, optimum CO2 concentration value was selected as 50 percent for the further tests.
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CO2 Sorption Capacity (mmol CO2/g-adsorbent)

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30% 50%

75% 100%
3

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0
0 50 100 150 -p 200 250 300 350 400
Time (sec)
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Figure 9 CO2 capture performances of TA0.24IL0.06 at various CO2 percent of inlet stream

Table 2 CO2 adsorption capacities of TA0.24IL0.06 at different percent of inlet stream


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Adsorption Adsorption
Adsorption time
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Sample ID CO2 (%) Capacity Capacity


(sec)
(mgCO2/g) (mmolCO2/g)
30 160± 0.13 81.55± 0.13 1.85± 0.13
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50 144± 0.24 81.55± 0.24 1.85± 0.24


TA0.24IL0.06
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70 140± 0.22 85.48±0.22 1.94± 0.22


100 180± 0.22 194.26± 0.18 4.41± 0.18

3.2.2. Effect of ionic liquid content at constant APTES ratio

Ionic liquid content of the prepared adsorbents were varied in order to evaluate their effect on the CO2
adsorption performances of amine-based silica aerogels. As observed from Figure 10 and Table 3, the
aerogels exhibited a progressive rise in CO2 capture capacities from 81.85 mg/g to 414.31 mg/g by
increasing the ionic liquid content from 0.06 to 0.28 in mole ratio. As proposed by Yu et al., ionic
liquid can capture CO2 through pyhsisorption mechanism based on the solubility of CO2 in the anion
group of ILs [30]. The relatively high solubility of CO2 in TF2N are related with the favorable
interactions between CO2 and fluoro alkyl substituent of the anion [75]. Therefore it can concluded
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that the increase in IL content in consideration of anion group (Tf2N), enhances the CO2 capture
capacities of the prepared samples, remarkably. The sample that contains 0.24 mol of APTES and
0.28 mol of IL (TA0.24IL0.28) ended up with the best result by reaching 243.32 mg/g (5.53 mmol/g)
CO2 adsorption capacity in 252 seconds.

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CO2 Sorption Capacity (mmol CO2/g-asorbent)

TA0.24IL0
5 TA0.24IL0.06
TA0.24IL0.15
TA0.24IL0.18
4 TA0.24IL0.28

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0 50 100 150 200 250 300 350 400
Time (sec.)
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Figure 10 CO2 capture performances of different ionic liquid containing aerogels at constant APTES
ratio
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Table 3 CO2 adsorption capacities of different ionic liquid containing aerogels


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Ionic liquid content Adsorption Capacity Capacity


Sample ID
(mol IL/mol TEOS) time (sec) (mgCO2/g) (mmolCO2/g)

TA0.24IL0 0.00 112± 0.34 91.08± 0.34 2.07± 0.34

TA0.24IL0.06 0.06 144± 0.24 81.55± 0.24 1.85± 0.24

TA0.24IL0.15 0.15 136±0.40 90.71± 0.40 2.06± 0.40

TA0.24IL0.18 0.18 196± 0.21 127.73± 0.21 2.90± 0.21


TA0.24IL0.28 0.28 252± 0.16 243.32± 0.16 5.53± 0.16
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3.2.3. Effect of APTES content at constant ionic liquid ratio

It is proposed by Vilarrasa-García et al that, CO2 in the gas stream can be chemically adsorbed by
primary amines of APTES through zwitterions mechanism to form carbamates [69]. Hence, APTES
content of the sample TA0.24IL0.28 was altered in order to investigate the effect of the amine ratio on
the CO2 adsorption capacity. The breakthrough behavior of the samples containing various amount of
APTES were obtained (Figure 11) and the CO2 adsorption capacities were evaluated correspondingly.
As it can be observed from Figure 11, there is a drastic decline on CO2 adsorption capacities with the
increase in the APTES mole ratio from 0.24 to 0.50, however, an insignificant change in the capacity
value were achieved by further increase in APTES content for the samples TA0.50IL0.28 and TA0.74IL0.28
(Table 4). This situation can be related with the contribution of the APTES involved in the sol gel

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synthesis step on the formation of the porous structure. Excess APTES addition during the preparation
stage resulted in the denser structure of samples by shortening gelation period. Moreover, low BET

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surface area and pore volume (Table 1) regarding highly condensed network, increased the diffusional
resistance in the sorption of CO2. Thus, CO2 sorption capacity of APTES containing samples
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decreased with the increase in APTES mole ratio.
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CO2 Sorption Capacity (mmol CO2/g-adsorbent)

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5
TA0.24IL0.28
TA0.5IL0.28
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TA0.74IL0.28
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0
0 50 100 150 200 250 300 350 400
Time (sec.)

Figure 11 CO2 capture performance of different APTES containing aerogels


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Table 4 CO2 adsorption capacities of aerogels containing various amount of APTES.

Adsorption time Capacity Capacity


Sample ID CO2 (%)
(sec) (mgCO2/g) (mmolCO2)/g)
TA0.24IL0.28 50 252± 0.16 243.32± 0.16 5.53± 0.16
TA0.50IL0.28 50 148± 0.32 76.4± 0.34 1.73± 0.34
TA0.74IL0.28 50 140±0.21 73.13±0.21 1.66± 0.21

CONCLUSION

Silica based aerogels containing various amount of ionic liquid and APTES were synthesized by using

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sol-gel method as a potential adsorbent for CO2 capture applications. The sorption capacities of the
prepared adsorbents are directly affected by the relative amount of IL and APTES which are

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incorporated on the porous structure. The synergetic effects of resultant materials on the CO2 capture
performance were obtained by combining different sorption mechanisms either pyhsisorption or
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chemisorptions arising from the diversity in the molecular structures of IL and APTES. CO2 capture
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were enhanced by the increase in IL content due to the favorable solubility of Tf2N anion of ILs. On
the other hand APTES incorporated on the structure, contributes the CO2 sorption capacity of the
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aerogels by means of chemisorptions mechanism. Sample of TA0.24IL0.28 having APTES and IL,
exhibited an appreciable CO2 adsorption performance with the capacity of 243.32 mg/g (5.53
mmol/g). It can be concluded that Ionic Liquid Containing Amine-Based Silica Aerogels can be used
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as the promising candidates as adsorbent for CO2 capture applications.


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ACKNOWLEDGMENT
This research was financially supported by The Scientific and Technological Research Council of
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Turkey (TUBİTAK) under contract No: 117M814.

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Declaration of interests

x The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:

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Author Statement

Müjde Garipoğlu: Investigation,Visualization, Writing - Original Draft

Nilay Gizli: Conceptualization, Supervision, Funding acquisition, Methodology, Writing - Original


Draft ,Writing, Review & Editing

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HIGHLIGTS

 silica based aerogels were synthesized by following single-step sol-gel method


 to enhance CO2 capture performances of aerogels, ionic liquid was used as sol agent
 CO2 adsorption capacities of aerogels increased with the addition of ionic liquid
 sorption capacities of the aerogels are affected by the amount of IL and APTES

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