Chemical Engineering Journal 262 (2015) 882–890

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Chemical Engineering Journal

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APTES grafted ordered mesoporous silica KIT-6 for CO2 adsorption

Rupak Kishor, Aloke Kumar Ghoshal ⇑
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 KIT-6 was synthesized and APTES

grafted in both dry and aqueous
solution.
 Role of water on APTES loading in
KIT-6 and grafting mechanism is
explained.
 APTES grafted KIT-6 exhibited a CO2
adsorption capacity of 0.90–
1.56 mmol g1.

a r t i c l e i n f o a b s t r a c t

Article history: Pure KIT-6 was synthesized using pluronic P123 (PEO20PPO70PEO20, mw  5800 Da) surfactant in mild
Received 15 August 2014 acidic condition. It was functionalized with (3-aminopropyl) triethoxysilane (APTES) by grafting in dry
Received in revised form 12 October 2014 and aqueous solvent at 80 °C. Cubic (Ia3d) structure and uniformity of the adsorbents were analyzed
Accepted 13 October 2014
by small angle powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy
Available online 22 October 2014
(HRTEM). Physical properties of the adsorbents were characterized by nitrogen adsorption/desorption
behavior, infrared spectroscopy (IR) and thermo gravimetric (TG) analysis. CO2 adsorption/desorption
Keywords:
behavior of the adsorbents was studied in a gravimetric analyzer. Optimum amine loading was substan-
KIT-6
Mesoporous silica
tially increased from 1.74 mmol N g1 in dry grafting to 2.75 mmol N g1 in aqueous grafting. The adsorp-
Grafting tion capacity was also remarkably increased from 0.90 mmol CO2 g1 (An_K_9.0A) to 1.56 mmol CO2 g1
APTES (Aq_K_0.20W_9.0A) at 30 °C. The heat of adsorption of the process was in the range of 20–32 kJ mol1.
CO2 adsorption The adsorbent showed its stability with the adsorption capacity remaining constant over 10 adsorp-
tion/desorption cycles.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction atmospheric concentration has already reached 400 ppm in

2014 and it will reach 450 ppm in next few years, which is suffi-
The rapid increase in global warming and its adverse effects on cient to increase global surface temperature above 2 °C of the max-
the environment, especially on the marine ecosystem has become imum limit range [2]. In the ‘‘United Nations Climate Change
a threat across the globe. According to earlier studies of paleocli- Conferences, Warsaw’’ (COP-19) countries have taken a strong
mate data and CO2 concentration in atmosphere, the rapid increase decision to control the global warming by CO2 capture and seques-
of global warming is mainly due to CO2 and other greenhouse gases tration (CCS) [3].
[1]. By observation of ‘‘Mauna Loa Observatory’’ Hawaii, CO2 Coal, oil and natural gas are the major sources of energy and
these provide 80% of world energy demand. These energy sectors
are the major anthropogenic sources of CO2 [4]. CCS is important
⇑ Corresponding author. Tel.: +91 361 2582252; fax: +91 361 2582291.
to mitigate the global warming and its consequences by capture
E-mail addresses: [email protected] (R. Kishor), [email protected]
of CO2 from large anthropogenic sources. Aqueous alkanolamines
(A.K. Ghoshal).

http://dx.doi.org/10.1016/j.cej.2014.10.039
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890 883

and chilled ammonia based absorption process [5,6], membrane interconnecting pores and may provide a better grafting surface for
separation process [7,8], novel cryogenic process [9], algal biomass amine and easy transport for the CO2 molecules [33,41]. As far as
process [10,11] and porous solid adsorption process [12–29] are we know, there is no report available on APTES modified KIT-6.
most commonly used for CO2 capture. Among these processes In this work we synthesized KIT-6 and functionalized it with vari-
aqueous alkanolamine especially monoethanolamine (MEA) and ous concentrations of APTES in dry and aqueous solution. The
diethanolamine (DEA) based absorption process is well known resulting materials were characterized through various techniques
with significant commercial application for CO2 capture. However and it was observed that the presence of water in the grafting solu-
corrosion of equipment and high cost of amine, large energy pen- tion influences the amine loading on KIT-6. The CO2 adsorption
alty for regeneration [30], loss of amine during regeneration [31], capacity measurements were performed in a gravimetric Rubo-
and impact of gaseous amine produced during regeneration on therm measurement set-up at various temperatures. Cyclic adsorp-
environment and eco-system [31,32] are reasons which make it tion/desorption capacity of the adsorbents were analyzed at 30 °C.
indispensable to see other alternative processes. Adsorption is an
alternate and cost effective CO2 capture process. In the recent years
microporous activated carbon [22,23], metal organic frameworks 2. Materials and methods
(MOFs), zeolites [24,25] and amine functionalized silica and foams
based adsorption processes [12–21,26–29] have shown strong 2.1. Synthesis of adsorbents
potential for CO2 capture.
Organosilane functionalized mesoporous silica viz. MCM, SBA, Traditional KIT-6 with 3D-cubic structure was synthesized by
MSU, silica foam and KIT-6 types have attracted great attention following the procedure of Kim et al. [41]. It was synthesized by a
of a large community of researchers for catalysis [33,34], support tri-block copolymer pluronic P123 surfactant (Sigma Aldrich) and
[35], radiotherapy [36], drug delivery [37] and acidic gas separa- n-butanol (Merck, P99%) as a directing agent in mild acidic condi-
tion [12–21] applications. It is well known that CO2 adsorption tion. Tetraethyl orthosilicate (TEOS, Merck, P99%) was used as a sil-
capacity is directly proportional to accessible amine groups on ica source in the synthesis of KIT-6. The molar composition of the
the silica surface. Primary amine directly reacts with CO2 and solution P123:TEOS:HCl:n-butanol:H2O was 0.017:1.0:1.83:1.31:1
forms carbamate via the formation of zwitterionic intermediates 95. In a typical synthesis process, 4.0 g of P123 was dissolved in
with maximum 0.5 mmol CO2 per mmol nitrogen of amine group. 144.0 g Millipore water and 7.9 g of HCl (Merck, 35%) solution. After
The carbamate formation mechanism was primarily explained by the solution became homogeneous, 4.0 g of n-butanol was added to
Caplow [38] and latter elaborated by several authors [16,18]. Load- the solution and mixed for an hour. TEOS (8.6 g) was added to the
ing of amino silane depends on the various conditions like surface solution and mixed for another 24 h. In all the synthesis steps, solu-
area, pore volume, pore size, grafting temperature, physical prop- tion mixture was maintained at 40 °C. Resulting mixture was trans-
erties of the material and grafting solvent. In most of the literature, ferred in Teflon autoclave and was hydrothermally treated at 100 °C
mesoporous silica was grafted in anhydrous solution [12–20]. for 24 h in static condition. Resulting solution was filtered and dried
However, amine loading increases in presence of water. To the best at 100 °C for 24 h in hot air oven. Organic surfactant was removed
of our knowledge, no literature is available till date regarding the by calcination at 550 °C for 5 h and resulting adsorbent was
work with APTES in presence of water. For instance, Pinto et al. denoted as K.
[39] showed the adsorption capacity 1.1 mmol CO2 g1 at 1 bar Pure silica was functionalized by grafting method, both in dry
and 25 °C for dry grafted APTES functionalized nano-porous silica and aqueous solution. In a typical dry grafting process, 1.0 g of K
using volumetric gas analyzer. Loganathan et al. [14] increased was dispersed in a 50 mL of dry toluene in a flask. In the resulting
the APTES loading by increasing the pore volume of MCM-41 and solution ‘x’ mmole of APTES was added and refluxed at 80 °C for
showed the CO2 adsorption capacity as 1.20 mmol g1 at 30 °C 24 h. The treated sample was filtered, washed with toluene and
using gravimetric measurement. Zeleňák et al. [12] studied the dried at 80 °C in vacuum for 16 h. The functionalized K was stored
CO2 adsorption at 25 °C with different loading of APTES and for further analysis and denoted as An_K_xA (where ‘x’ represents
reported that the adsorption capacity of CO2 increases the concentration of APTES in mmol g1). In aqueous grafting, ‘y’
(0.57 mmol g1 for MCM-41, 1.04 mmol g1 for SBA-12 and mL of water was added in the dispersed K solution and stirred
1.54 mmol g1 for SBA-15) with increasing in pore size in the order for 2 h at room temperature. Optimized concentration of APTES
of MCM-41 (3.3 nm) < SBA-12 (3.8 nm) < SBA-15 (7.1 nm). Wang from dry grafting process was added in the solution and refluxed
et al. [15] increased the aminosilane loading and CO2 adsorption at 80 °C for 24 h. Other steps were similar as explained above
capacity by increasing the surface silanol density by removal of and the functionalized material was denoted as Aq_K_yW_xA.
template using ethanol extraction of uncalcined silica. Ko et al.
[16] modified the SBA-15 by primary, secondary and tertiary
amines and reported the adsorption capacity of 0.95, 0.75 and 2.2. Adsorbent characterization
0.17 mmol g1 respectively for these amines at 25 °C. Liu et al.
[28] functionalized the KIT-6 by tetraethylenepentamine using Mesoporous material structure of K, dry solution grafted
wet-impregnation method and showed an adsorption capacity An_K_xA and aqueous solution grafted Aq_K_yW_xA adsorbents
2.9 mmol g1 at 60 °C using gas chromatograph (GC) with a 10% were characterized by powder X-ray diffractometer (XRD, Bruker,
CO2 in feed gas. Linneen et al. [40] functionalized the aerogel with D8 Advance) with Cu Ka radiation (power 40 kV, 40 mA). Surface
APTES using grafting method and showed the CO2 adsorption morphology was measured by TEM (JEOL JEM-2100 at 200 kV).
capacity 0.67 mmol g1 at 1 bar and 25 °C. Recently, Zhang et al. Physical properties of the adsorbent were measured by nitrogen
[29] studied the CO2 sorption in wet KIT-6 at high pressure adsorption/desorption isotherm (Quantachrome autosorb iQ) at
(4.5 MPa). There was a sharp increase in adsorption capacity 196 °C. The Brunauer–Emmett–Teller surface area (SBET) was
due to condensation of CO2 in mesoporous channels. calculated over relative pressure range (P/P0) 0.05–0.30 and pore
Thus, there have been numerous literatures reported on CO2 volume at 0.99. Pore size distributions were determined by Bar-
adsorption in amine grafted MCM and SBA series. But only few of rett–Joyner–Halenda (BJH) method of nitrogen adsorption curve.
them concentrate on the CO2 adsorption behavior in KIT-6. Functional groups present in the adsorbent were analyzed by
MCM-41 and SBA-15 have 2D hexagonal structure with parallel diffuse reflectance infrared Fourier transform (DRIFT) spectra (IR-
cylindrical pore whereas KIT-6 has 3D cubical structure with large Affinity, Shimadzu) and amount of APTES grafted was examined
884 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890

by thermo gravimetric(TG) analyzer (Netzsch Sat) in the tempera-

ture range of 25–800 °C with a heating rate 10 °C min1.

2.3. CO2 adsorption and desorption measurement

Adsorption and desorption measurements of CO2 on K, An_K_xA

and Aq_K_yW_xA adsorbents were performed using a Rubotherm
gravimetric magnetic suspension balance at different temperatures
for pressure till 5 bar. A definite amount of adsorbent was placed in
a sample holder and suspended with a magnetic balance. Sample
was closed by external fitting. Initially, adsorbent was outgassed
at 120 °C in helium atmosphere to remove the unwanted gas and
moisture present, subsequently the sample was cooled to 30 °C.
CO2 was inserted in the sample chamber till desired pressure
was reached and waits for 20 min for the system to reach thermo-
dynamic equilibrium. The change in weight, pressure and temper-
ature were measured continuously for every pressure point and
the adsorption capacities at temperatures 30, 45, 60 and 75 °C
were evaluated. All the experimental measurements were carried
out in triplicates and the average value are reported. In a typical
kinetic measurement, CO2 was purged into the sample chamber
with a step input at 1 bar pressure. Cyclic adsorption/desorption
capacities of the materials were analyzed at 30 °C and regeneration
was done at 120 °C in helium atmosphere.

3. Result and discussion

3.1. Material characterization

The XRD pattern of K confirmed the gyroidal cubic Ia3d struc-

ture with d211 and d220 plane of the material [41,42]. In dry and
aqueous solution grafted adsorbents An_K_xA and Aq_K_yW_xA
show nearly same Bragg’s diffraction peak d211 but intensities are Fig. 2. Nitrogen adsorption/desorption isotherm of (a) K and dry grafted An_K_xA
sparsely reduced with increase in the APTES concentration as and (b) Aqueous grafted Aq_K_yW_9.0A.
shown in Fig. 1. In addition, for Aq_K_yW_xA cases, peak intensity
was drastically decreased. This indicates that the regularity of the
according to the IUPAC classification, which is the characteristic of
silica materials is preserved after APTES loading both in dry and
mesoporous materials [15,41]. Physical properties like specific sur-
aqueous solution grafting processes but internal surface of the pore
face area (SBET), pore volume (Vt) and pore diameter (dBJH) of the
and external surface of the adsorbent are occupied by amine.
materials are summarized in Table 1. With increase in the APTES
Nitrogen adsorption/desorption isotherm and BJH pore size dis-
concentration in solution from 7.0 to 11.0 mmol g1, SBET and Vt
tribution of pure and APTES grafted (dry and aqueous) adsorbents
of K are decreased drastically from 711 to 285 m2 g1 and from
are depicted in Fig. 2a and b. The nitrogen adsorption isotherms for
1.05 to 0.59 cm3 g1 respectively [12–16]. This indicates that some
K, An_K_xA and Aq_K_yW_xA are of type IV with a hysteresis loop
pore volume and area are still available for amine loading. Further,
with increase in the volume of water from 0.15 to 0.25 mL in opti-
mum APTES grafted adsorbent, specific surface area and pore vol-
ume of the adsorbent decrease sharply from 297 to 12 m2 g1
and from 0.62 to 0.05 cm3 g1 respectively due to higher amount
of APTES loading. HRTEM images of KIT-6 showed well-ordered
and alternating pore channels (Fig. 3a and b) and similar to the
results observed in literature [41,42]. After grafting in dry amine
solution, shrinkage of pore channels was observed in the adsor-
bent. In aqueous amine solution grafting, maximum pore volume

Table 1
Structural properties of materials.

Sample SBET (m2 g1) Vt (cm3 g1) dBJH (nm)

K 711 1.05 8.04
An_K_7.0A 304 0.68 7.35
An_K_9.0A 297 0.62 7.34
An_K_11.0A 285 0.59 7.34
Aq_K_0.15W_9.0A 95 0.26 4.97
Aq_K_0.20W_9.0A 90 0.22 4.83
Fig. 1. XRD pattern of (a) K, (b) An_K_7.0A, (c) An_K_9.0A, (d) An_K_11.0A, (e) Aq_K_0.25W_9.0A 12 0.05 4.80
Aq_K_0.15W_9.0A, (f) Aq_K_0.20W_9.0A and (g) Aq_K_0.25W_9.0A.
 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890 885

Fig. 3. HRTEM image of (a) and (b) pure K, (c) An_K_9.0A and (d) Aq_K_0.20 W_9.0A.

was utilized and no damage of the structure was observed after and peak across 800 cm1 are attributed to the asymmetric
grafting as shown in Fig. 3c and d. and symmetric stretch of siloxane groups, respectively, and the
Amount of APTES and thermal stability of An_K_xA and peak at 960 cm1 corresponds to the free silanol group of mesopor-
Aq_K_yW_9.0A were analyzed by TG analyzer and the results are ous silica [44–45]. The broad peak at 3200–3600 cm1 represents
shown in Fig. S1 (Supplementary data). The total mass loss in the the hydrogen bonded surface silanol groups, and at 3740 cm1
adsorbents is grossly occurred in two steps. The mass loss in the for single and geminal silanol groups of K. The other peaks at
first stage, (temperature range 25–200 °C) was due to liberation 1620 cm1 and 2360 cm1 represents the physically adsorbed
of moisture, adsorbed gases and isolated APTES molecules water and CO2 respectively [46]. In APTES grafted adsorbents, the
[15,19]. The mass loss in second stage (200–600 °C), corresponds peaks around 1485 cm1 and 1567 cm1 represent the –NH2
to the degradation of grafted amine [19,43]. The total mass loss and –NH– groups associated with the surface [47]. The peak inten-
in this temperature range was 8.31% for An_K_7.0A, 8.68% for sity was found higher in case of aqueous grafted adsorbents when
An_K_9.0A, 9.98% for An_K_11.0A, 12.48% for Aq_K_0.15W_9.0A, compared to dry grafted adsorbents which confirm the higher APTES
14.17% for Aq_K_0.2W_9.0A, and 15.48% for Aq_K_0.25W_9.0A loading in aqueous grafting. The bands around 2876 cm1 and
which correspond to APTES content of 1.43, 1.50, 1.72, 2.15, 2.44 2930 cm1 correspond to the symmetric and asymmetric deforma-
and 2.67 mmol N g1 of adsorbent (Table 2). With increasing the tion of the CH2 groups of propyl chain present in APTES [48].
concentration of APTES in the dry grafting process from 7.0 to
11.0 mmol g1 adsorbent, loading of amine is increased in follow- 3.2. CO2 adsorption on APTES grafted adsorbents
ing order An_K_7.0A < An_K_9.0A < An_K_11.0A. In case of aqueous
grafting, with increasing the water content from 0.15 to 0.25 mL in To begin with, the effect of APTES loading in pure KIT-6 was
the mixture increased the amine loading in the following order analyzed by CO2 adsorption capacity at different temperatures
Aq_K_0.15 W_9.0A < Aq_K_0.20W _9.0A < Aq_K_0.25W_9.0A. and pressures to compare with other adsorbents. Adsorbent with
The DRIFT spectra were recorded in the range 500–4000 cm1 different APTES loading ranging from 1.60 to 1.92 mmol g1 were
to confirm the APTES in the adsorbents as shown in the Fig. S2 synthesized in dry toluene and tested for the CO2 adsorption. The
(Supplementary data). The band across 1040 to 1250 cm1 adsorption isotherms at 30 °C are shown in Fig. 4a and b. All iso-
therms clearly indicate the increase in CO2 adsorption capacity
with increasing pressure. In low pressure region (<0.20 bar) a sharp
Table 2
CO2 adsorption capacities of amine functionalized adsorbents.
increase in adsorption capacity was observed attributed to the
chemisorption between CO2 and amine functional group present
Sample APTES Adsorption Adsorption efficiency on the surface in both dry and aqueous grafted adsorbents. The
loading capacity at 1 bar (mmol CO2 mmol1 N)
(mmol N g1) (mmol CO2 g1)
equilibrium adsorption capacities at 1 bar follow the order
K < An_K_7.0A < An_K_11.0A < An_K_9.0A at 30 °C (Table 2). The
K – 0.48 –
An_K_7.0A 1.43 0.76 0.53
maximum adsorption capacity of 0.90 mmol CO2 g1 is observed
An_K_9.0A 1.50 0.90 0.60 in An_K_9.0A at 1 bar. Although APTES loading is maximum
An_K_11.0A 1.72 0.83 0.48 (1.72 mmol N g1) on An_K_11.0A adsorbent, adsorption capacity
Aq_K_0.15W_9.0A 2.15 1.26 0.58 is less compared to An_K_9.0A. It clearly indicates that adsorption
Aq_K_0.20W_9.0A 2.44 1.56 0.64
capacity is not increased even at higher amine loading. This sug-
Aq_K_0.25W_9.0A 2.67 0.32 0.12
gests that, in higher APTES concentration amine groups are over-
886 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890

centration on CO2 adsorption is shown in Fig. 4. CO2 adsorption is

less in case of dry solution grafted adsorbents when compared to
the aqueous solution grafted one. Thus, the optimum amine load-
ing and CO2 adsorption depends on the kind of grafting process.
The amine loading is found to have increased with increase in
APTES concentration (Table 2) in dry solution grafting because,
ethoxy group of silane directly reacts with surface silanol groups
(single, hydrogen-bonded and geminal silanol group) via conden-
sation reaction (Scheme 1a) and formed a monolayer over the
surface [51]. On the other side, aqueous grafting is more com-
plex than dry grafting over silica as the reaction mechanism pro-
ceeds via hydrolysis followed by double condensation reaction
(Scheme 1b) [43,50,51]. Hydrophilic aminosilanes instantly hydro-
lyzed in presence of water and grafted over silica surface. During
aqueous grafting, amine loading follows the order Aq_K_0.15-
W_9.0A < Aq_K_0.20W_9.0A < Aq_K_0.25W_9.0A with increasing
the concentration of water from 0.15 to 0.25 mL.
Thus, on the basis of above results, we summarized the mecha-
nism of APTES grafting and distribution onto adsorbents as follows.
In dry grafting, APTES molecules diffuse into mesopore (>2 nm) of
pure K and get uniformly grafted (Fig. 5a). In aqueous grafting
APTES oligomers diffuse in the pore and get grafted over surface
(Fig. 5b). For longer times periods in aqueous solution it formed
multilayers of aminosilane. In contrast, with higher water concen-
tration higher molecular weight oligomers were formed in the
solution and which blocked the pores (Fig. 5c) [50].
At low pressure, the interaction between CO2 with grafted
amine by chemisorption could be explained by Caplow mechanism
[17,38]. Dry CO2 (Lewis acid) directly reacts with basic amine
groups present on the surface of adsorbent via zwitterion interme-
diate and produce carbamate as shown in Reaction (1).

CO2 þ —NH2 ! —NHþ2 COO ; —NHþ2 COO þ —NH2

! —NHCOO þ —NHþ3 ð1Þ
Adsorption efficiency for monoamine is the ratio of number of
Fig. 4. CO2 adsorption capacities at 30 °C for different APTES functionalized mmol of CO2 adsorbed per mmol of amine [16]. In overall adsorp-
adsorbents (a) An_K_xA and (b) Aq_K_yW_9.0A. tion Reaction (1), each mmol CO2 requires two mmol amine with
maximum possible efficiency is 0.5. The adsorption efficiency of
the adsorbents An_K_xA and Aq_K_yW_9.0A lies between 0.48–
lapped with each other and reduce the accessible amine groups for
0.60 mmol CO2 mmol1 N and 0.12–0.64 mmol CO2 mmol1 N
CO2 surface area of the adsorbent [49].
respectively (Table 2). The efficiency of amine grafted adsorbents
Presence of water in the grafting solution shows dramatic
is higher at higher pressure, which might be possible due to the
change in the attachment of APTES on the adsorbents and CO2
combined effects of chemisorption and physisorption between
adsorption capacity. The adsorbents synthesized in presence of
adsorbate and adsorbent. The adsorption efficiency of
water (y = 0.15–0.25) show higher adsorption capacity in following
Aq_K_0.25W_9.0A is quite low (0.12 mmol CO2 mmol1 N) as com-
order Aq_K_0.25W_9.0A (0.32 mmol CO2 g1) < Aq_K_0.15W_9.0A
pare to others which may be due to the blockage of the pores as
(1.26 mmol CO2 g1) < Aq_K_0.20W_9.0A (1.56 mmol CO2 g1) at
mentioned earlier.
1 bar and 30 °C (Table 2). The adsorption capacities of
Aq_K_0.15W_9.0A and Aq_K_0.20 W_9.0A are increased with the
maximum at 0.20W. Any further increase in the water content
3.4. CO2 adsorption kinetics
i.e. Aq_K_0.25W_9.0A decreased the adsorption capacity signifi-
cantly even with higher amine loading. This suggests that when
Dynamic CO2 adsorption isotherm of the optimum amine
grafting is done in presence of higher water concentration, less
grafted adsorbents (in dry and aqueous conditions) is shown in
amine groups are accessible in the adsorbent for CO2. This is possi-
Fig. 6. It was observed that the CO2 adsorption capacity of K,
bly because APTES had oligomerized in the solution and even
An_K_9.0A and Aq_K_0.20W_9.0A are 0.48, 0.90 and
closed the pore of the adsorbent during grafting [50]. In low water
1.56 mmol g1 respectively at 1 bar and 30 °C. It may be noted that
concentration, the APTES oligomer might not grow enough inside
in first few minutes adsorption isotherm is sharply increased due
the pores and thus resulting in more CO2 adsorption.
to chemisorption between CO2 and amine. About 90.0% of the ulti-
mate adsorption capacity is reached within initial 10 min and after
3.3. Grafting mechanism of APTES and CO2 interaction 20 min reached the equilibrium. The adsorption capacities of
APTES grafted KIT-6 with other adsorbents analyzed using differ-
Optimum amine concentration onto adsorbent minimizes the ent analytical techniques available in the literature are summa-
capex and opex of CO2 capture process. CO2 adsorption capacity rized in Table 3. From table it can be observed that KIT-6 showed
of pure K was 0.48 mmol g1 at 1 bar and 30 °C attributed to the better adsorption capacity compared to other adsorbents present
physisorption of CO2 on the silica surface. The effect of amine con- in literature except PE-MCM-41 and HTT-32.
 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890 887

Scheme 1. Grafting mechanism of APTES in (a) An_K_9.0A and (b) Aq_K_0.20W_9.0A.

Fig. 5. Schematic of APTES loading in KIT-6.

3.5. Effect of the temperature on CO2 adsorption

The adsorption capacities of K, An_K_9.0A and

Aq_K_0.20W_9.0A at various temperatures (30, 45, 60 and 75 °C)
are depicted in Fig. 7. The adsorption capacities at 1 bar of K,
An_K_9.0A and Aq_K_0.20W_9.0A were found to be 0.48, 0.33, Fig. 6. Dynamic adsorption performance of K, optimum amine loaded An_K_9.0A
0.24, 0.19 mmol CO2 g1, 0.90, 0.73, 0.63, 0.55 mmol CO2 g1, and and Aq_K_0.20W_9.0A adsorbents.
888 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890

Table 3
Comparison of the literature data and the current results for CO2 adsorption capacities of APTES functionalized adsorbents.

Adsorbent Pressure (bar) Temperature (°C) Method mmol CO2 g1 adsorbent References
MCM-41 1.0 30 MB 1.15 [16]
SBA-12 1.0 25 TGA 1.04 [17]
SBA-12 0.10 25 TGA 0.46 [17]
MCM-48 1.0 25 MB 0.80 [18]
PE-MCM-41 1.0 30 TGA/MS 2.70 [19]
HTT32 1.0 25 VA 2.41 [40]
MCM-41 1.0 25 GA 1.20 [12]
SBA-15-cal 1.0 25 TGA 1.54 [13]
MCM-48 0.05 25 VA 1.02 [15]
PCH 1.0 25 VA 1.10 [36]
CNT 1.0 27 GC 0.93 [20]
Silica gel 1.0 30 VA 0.41 [52]
Xerogel 1.0 30 TGA 1.10 [53]
Aerogel 1.0 25 MB 0.67 [37]
An_KIT-6 0.15 30 GA 0.56 Present study
Aq_KIT-6 0.15 30 GA 1.28 Present study
An_KIT-6 1.0 30 GA 0.90 Present study
Aq_KIT-6 1.0 30 GA 1.56 Present study

MB: micro balance, TGA: thermogravimetric analysis, MS: mass spectrometer, GC: gas chromatography, VA: volumetric apparatus, GA: gravi-
metric analysis.

Fig. 7. Adsorption isotherms of (a) K (b) An_K_9.0A and (c) Aq_K_0.20W_9.0A at 30, 45, 60 and 75 °C.

1.56, 1.50, 1.44, 1.31 mmol CO2 g1 at 30, 45, 60 and 75 °C respec- temperature of the adsorption process. The value of DH° for K,
tively. It is observed that the adsorption capacity decreases with An_K_9.0A and Aq_K_0.20W_9.0A are 20.21, 33.18 and
increasing the temperature and is related to the exothermic inter- 31.26 kJ mol1 respectively. The DH° value is low in pure K
action between CO2 and adsorbent [15]. The amount of heat due to physisorption between CO2 and silica surface and well com-
evolved in CO2 adsorption process is estimated by Clausius– parable with earlier reported value (22–23 kJ mol1) [55]. The heat
Clapeyron equation in form of isosteric heat of adsorption of adsorption value of amine grafted adsorbents is significantly
(DH°) [54]. It is calculated from slope of the ln (P) vs (1/T) curve higher due to strong interaction (chemisorption) between CO2
(Fig. S3, Supplementary data) for the same adsorbed amount, and amine sites. The calculated value of DH° for amine grafted
where P and T are represents the applied CO2 pressure and adsorbents An_K_9.0A and Aq_K_0.20W_9.0A is 33.21 and
 R. Kishor, A.K. Ghoshal / Chemical Engineering Journal 262 (2015) 882–890 889

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