Microporous and Mesoporous Materials 116 (2008) 358364

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Amine-modied SBA-12 mesoporous silica for carbon dioxide capture:

Effect of amine basicity on sorption properties
V. Zelenak a,*, D. Halamova a, L. Gaberova b, E. Bloch b, P. Llewellyn b
a
b

Institute of Chemistry, Department of Inorganic Chemistry, Faculty of Science, P. J. Safarik University, Moyzesova 11, SK-041 54 Kosice, Slovak Republic
Laboratory Madirel, Centre de St. Jrme, CNRS-Universit de Provence, Marseille, France

a r t i c l e

i n f o

Article history:
Received 12 July 2007
Received in revised form 7 March 2008
Accepted 22 April 2008
Available online 27 April 2008
Keywords:
Mesoporous silica
SBA-12
Solid amine sorbents
Carbon dioxide

a b s t r a c t
SBA-12 mesoporous silica was modied by 3-aminopropyl (AP), 3-(methylamino)propyl (MAP) and
3-(phenylamino)propyl (PAP) ligands. The electronic effects in AP, MAP and PAP ligands resulted in different surface basicity of the modied silica materials. The materials were characterized by thermogravimetry, X-ray powder diffraction, nitrogen adsorption/desorption and transmission electron microscopy. The
CO2 sorption/desorption experiments performed at 25 oC by gravimetric method showed that carbon
dioxide sorption capacities were 1.04 mmol/g for the sample SBA-12/AP, 0.98 mmol/g for the sample
SBA-12/MAP and 0.68 mmol/g for the sample SBA-12/PAP. The modied silica can be regenerated by purge
with inert gas without heating. The fastest desorption was observed for the SBA-12/PAP silica containing
amine of low basicity (pKb = 8.9). The desorption process of SBA-12/AP and SBA-12/MAP samples was
accompanied by consumption of heat evolved on adsorption, while no thermal effect was recorded on
the DTA curve of SBA-12/PAP sample.
2008 Elsevier Inc. All rights reserved.

1. Introduction
Carbon dioxide is one of the greenhouse gases whose increasing
concentration in the atmosphere is proposed to have direct linkage
to global climate changes. A great deal of effort is nowadays devoted in limiting the emissions of greenhouse gases to environment. Generally, there are three steps in CO2 management:
separation, transportation and sequestration [1,2]. Various strategies have been proposed to sequester carbon dioxide including
recently invoked sequestration by injecting carbon dioxide directly
into underground geological formations, old mines or caverns
[36]. However the key point for the sequestration is the removal
of CO2 from ue gas by a gas separation process prior to its release
to the atmosphere. The separation cost constitutes about threefourths of the total cost [1,2]. Therefore it is important to nd an
efcient and economic route to capture and separate carbon dioxide produced during various industrial processes.
At present the separation of CO2 is achieved by using solvents,
cryogenic techniques, membranes and solid sorbents [710]. The
chemical absorption by liquid alkanolamines is the most widely
developed commercial technology for CO2 separation [11]. The
reaction sequences in such systems involve formation of ammonium carbamate species under anhydrous conditions and their
transformation to ammonium bicarbonate and carbonate species
* Corresponding author.
E-mail address: vladimir.zelenak@upjs.sk (V. Zelenak).
1387-1811/$ - see front matter 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.04.023

in the presence of water. However, the use of liquid amines has

several drawbacks like high energy consumption, solvent regeneration, large dilutions with water required to prevent equipment
corrosion or ow problems caused by viscosity [11].
An attachment of amine functional groups onto high surface
area solids may help to overcome some of these limitations. Immobilized amine solid sorbents based on polymers are already used in
aircraft, submarine, and spacecraft technologies [12]. A group of
the solids, which could be advantageously used for the modication with amines, are ordered mesoporous silicas. These materials
possess long-range order, well-dened regular pore structures in
the mesopore range and large surface areas. Therefore after surface
modication such materials can take advantage of high surface
area and high selectivity to carbon dioxide.
In recent years several studies dealt with the preparation and
characterization of amine-modied mesoporous silica materials
for carbon dioxide capture. In works of Yogo et al. [13,14] SBA-15
mesoporous silica was grafted by various aminosilanes, namely
aminopropyltriethoxysilane (APS), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPS), (3-trimethoxysilylpropyl)diethylenetriamine (TA). The efciencies of the aminosilanes at identical
surface density of amine were found to be in the order APS >
AEAPS > TA [13]. Carbon dioxide adsorption capacities were reported as 0.52, 0.87, and 1.10 mmol/g for the monoamino, diamino,
and triamino grafted SBA-15 supports, respectively [14]. The group
of Yogo also studied amine-modied mesoporous silica membranes, which showed high CO2 permselectivity [15].

V. Zelenak et al. / Microporous and Mesoporous Materials 116 (2008) 358364

359

Scheme 1.

Huang et al. studied the adsorption properties of MCM-48 silica

grafted by 3-aminopropyltriethoxysilane [16]. The adsorption
capacities in dry conditions were determined as 1.14 mmol/g (5.0
wt%). When the sorbent was exposed to a humid stream of 5%
CO2/N2, the adsorption capacity for CO2 doubled [16].
Kim et al. studied several types of amine groups attached on the
surface of MCM-48 and their inuence on CO2 sorption over the
modied materials [17]. They used aminopropyl (monomeric,
unhindered), pyrrolidinepropyl (monomeric, hindered), polymerized aminopropyl (polymeric, unhindered) and polyethylenimine
(polymeric, hindered) amines for the study. MCM-48 silica containing polymeric amines showed higher concentration of amine
sites but the monomeric aminopropyl-attached MCM-48 silica displayed a higher CO2 adsorption rate because of greater accessibility
to amine adsorption sites [17].
Conventional MCM-41 and pore-expanded MCM-41 (PE-MCM41) silica have been used as supports for grafting of diethanolamine (DEA) and 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane (TRI) in the works of Sayari [18,19]. PE-MCM-41
has been shown to have higher adsorption capacities compared
to standard MCM-41 silica.
A series of diethylenetriamine[propyl(silyl)] (DT) functionalized
silicas were prepared by modication of mesoporous silica substrates
with N-[3-(trimethoxysilyl)propyl]-diethylenetriamine [20,21]. The
DT-functionalized materials were found to have greater CO2 adsorption capacities than the analogous aminopropylsilyl (AP) and ethylenediamine[propyl-(silyl)] (ED) functionalized materials. However
the DT-functionalized samples achieved lower amine efciencies
than the analogous AP- and ED-functionalized materials [20,21].
It is obvious that different types of ordered mesoporous silica
(MCM-41, MCM-48, SBA-15) as well as different amines were tested
as materials for carbon dioxide sorption. As the carbon dioxide sorption on these materials is governed by acidbase interactions among
molecules of carbon dioxide as acidic gas, and the amines as basic
centres, we have investigated the inuence of basicity of amine ligands on sorption of carbon dioxide over amine-modied mesoporous silica. We have modied SBA-12 silica by three kinds of amines
namely 3-aminopropyl, 3-(methylamino)propyl or 3-(phenylamino)propyl (see Scheme 1). The present work deals with the characterization of the prepared materials and study of carbon dioxide
sorption on these materials by gravimetric method.
2. Experimental
All chemicals were purchased from Aldrich and used as received
without further purication. Tetraethoxysilane (TEOS) was used as
silica source and Brij 76 (C18EO10; EOCH2CH2O) as a structure
directing agent. 3-Aminopropyl (hereafter referred as AP), 3-(methylamino)propyl (referred as MAP) and 3-(phenylamino)propyl (referred as PAP) were used for the silica modication (see Scheme
1). The respective trialkoxysilanes were sources of AP, MAP and PAP.
2.1. Preparation of the SBA-12 mesoporous silica and its modication
In a typical synthesis Brij 76 was mixed with water and hydrochloric acid. The mixture was heated to 50 oC. Then TEOS was

added under vigorous stirring (500 rpm) and the resulting mixture
was stirred for 1 day at 50 oC. After this time the mixture was aged
under static conditions at 80 oC. The HCl/H2O/Brij 76/TEOS molar
ratio was 26.7/910.6/1/7.3. The solid product was ltered off,
repeatedly washed with distilled water and dried at room temperature. The surfactant was removed by calcination in air ow at
500 oC for 7 h.
The surface modication of the calcined SBA-12 was carried out
by grafting. Prior to grafting the mesoporous silica was dehydrated
at 200 oC for 3 h not to remove surface hydroxyls but adsorbed
moisture. Then 1 g of SBA-12 was dispersed in 50 cm3 of toluene
dried over zeolite sieve. 3 cm3 of the respective amine (AP, MAP
or PAP) were added to toluene and suspension was kept under reux for 20 h. The solid product was ltered off, repeatedly washed
with toluene and octane and dried at 80 oC.
2.2. Characterization
The XRD patterns were measured on a Philips PW1710 diffractometer using Co Ka radiation (1.790307 ). Infrared spectra were
recorded using Avatar FT-IR spectrometer. Thermal characterization was carried out using STA Netzch 409PC apparatus under dynamic conditions with heating rate 9 oC/min in atmosphere of air
(20 cm3/min). Nitrogen adsorption/desorption experiments were
measured with a Quantachrome Autosorb Automated Gas Sorption
System at 77 K. Prior to adsorption, samples were outgassed under
vacuum for 24 h at 110 oC. The HRTEM micrographs were taken
with a Jeol 3000 microscope. Elemental analyses were performed
with FlashEA 1112 elemental analyser (ThermoFinnigan).
The CO2 sorption capacities were determined by a thermogravimetric balance Netzch 409PC using the sample sizes of 10 mg. The
10% CO2/N2 certied gas mixture, purchased from Linde gas, was
used for the sorption study. The composition of the mixture resembled the concentration of CO2 in the ue gas, where concentration
is ranging from 10% to 15% [22]. The ow rate of CO2/N2 mixture
was 20 cm3/min. Initial activation of the grafted samples was performed by heating in inert gas (Ar) to 110 oC.
3. Results and discussion
3.1. Characterization of SBA-12 mesoporous matrix
Fig. 1 shows the XRD pattern of calcined SBA-12 mesoporous
silica. A strong peak with d-spacing of 49.8 , typical of SBA-12
material [23], was observed in the XRD pattern. The pattern avoids
an unequivocal assignment of the symmetry due to the presence of
only one peak. The HRTEM micrographs showed predominantly
hexagonal phase, with small fraction of cubic phase (upper right
part of Fig. 2a), showing intergrowth of hexagonal (hcp) and cubic
(ccp) phases, typical for SBA-12 material [23,24]. Fig. 2 shows that
the prepared material has an excellent periodicity of mesopores
with mean pore size approximately 3.5 nm.
Nitrogen adsorption/desorption isotherms of SBA-12 sample
(Fig. 3) are of type IV without hysteresis. The initial part of the
adsorption isotherm corresponds to adsorption in the micropores
and formation of the multilayer lm on the pore walls. The

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V. Zelenak et al. / Microporous and Mesoporous Materials 116 (2008) 358364

Fig. 1. XRD pattern of SBA-12 mesoporous silica.

Fig. 3. Nitrogen adsorption/desorption isotherms of SBA-12 sample.

isotherm shows a well dened adsorption/desorption step between partial pressures P/P0 of 0.20.4, indicative of the lling of
mesopores. The prepared SBA-12 has well-dened uniform pore
dimensions, with an average pore size of 38 and a pore volume
0.842 cm3/g. BET surface area was 1347 m2/g.
3.2. Characterization of amine-modied materials
The XRD measurements of the modied materials showed that
long-range order of the materials was retained after the modication (see Fig. 4). The diffraction peaks of grafted materials occur at
similar angle in comparison with pure SBA-12, indicating no substantive change in the mesoporous matrix after silanization treatments. The decrease of intensity of diffraction peak in grafted
materials was observed due to partial lling of the mesopores by
the amines [2,21].
The modication of the SBA-12 silica signicantly affected the
N2 uptake and BET surface area in the modied materials (Fig. 5).
The sorption experiments yielded BET surface area of 416 m2/g
for SBA-12/AP sample, 317 m2/g for SBA-12/MAP and 381 m2/g
for SBA-12/PAP sample. The pore radius in the grafted samples
was about 1.2 nm.
The thermal stability of the samples was characterized by thermogravimetric analysis. Fig. 6 shows TG/DTA curves of SBA-12/AP,
SBA-12/MAP and SBA-12/PAP samples during heating in air. The
mass loss between room temperature and 200 oC corresponds to
liberation of adsorbed moisture. It is to note, that mass loss in this

Fig. 4. XRD patterns of SBA-12/AP, SBA-12/MAP and SBA-12/PAP samples. The

patterns are offset for clearer comparison.

temperature range decreases with the hydrophobicity of the amine

ligands. The observed mass loss up to 200 oC was about 4% for the
samples SBA-12/AP and SBA-12/MAP while for the sample SBA-12/
PAP, containing the phenyl ring, the observed mass loss up to
200 oC represented only 0.8 wt.%. On further heating the pyrolysis

Fig. 2. TEM micrographs of SBA-12 mesoporous silica.

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V. Zelenak et al. / Microporous and Mesoporous Materials 116 (2008) 358364

Fig. 5. Nitrogen adsorption isotherms of AP, MAP and PAP modied SBA-12 silica.

of amine ligands took place and the decomposition was complete

by 700 oC. The process of decomposition is divided in two poorly
separated steps and it is accompanied by exothermic peaks at
290 and 617 oC for the sample SBA-12/MAP, 310 and 630 oC for
the sample SBA-12/AP and 332 and 595 oC for the sample SBA12/PAP. From the results of TGA it was possible to estimate amount
of amines grafted on the surface of SBA-12. The mass loss in the
temperature range 200700 oC represents 15.2% for the sample
SBA-12/AP, 17.3% for the sample SBA-12/MAP and 22.9% for the
sample SBA-12/PAP. We could consider that the highest amine
loading was achieved for the sample SBA-12/PAP. However we
have to take into account the different molar masses of AP, MAP
and PAP as well as the fact that the amine surface density is the

important characteristics inuencing sorption properties of carbon

dioxide on the modied materials. The amine surface densities
were calculated from the nitrogen content in the samples as assessed from elemental analysis and the results are summarized
in Table 1. According these values the highest sorption capacity
should be expected for the SBA-12/MAP sample while the SBA12/PAP silica should exhibit lowest sorption capacity.
Infrared spectra of the modied materials are shown in Fig. 7.
The bands of the CH stretching vibrations of propyl chains were
observed around 2930 cm1 for all three samples. The aromatic
m(CH) stretches in SBA-12/PAP modied silica were found around
3050 cm1 and the deformation d(CH) vibrations of metyl group
in SBA-12/MAP sample were observed at 1473 cm1.
The SiOSi bands of mesoporous matrix dominated the spectra
of all samples. These bands were observed at about 1100 cm1
(shoulder at 1220 cm1) due to asymmetric SiOSi stretch and
at about 792 cm1 due to symmetric SiOSi stretch.
The main differences between infrared spectra of respective
samples were recorded in the region 16401400 cm1. The band
of the bending vibration of water, d(HOH), observed around
1639 cm1 was clearly identied in the SBA-12/AP and SBA-12/
MAP samples, while in SBA-12/PAP sample only a shoulder was observed. This agrees with the results of thermal analysis mentioned
above showing that water content in the samples decreases with
hydrophobic character of the amine ligands. The bands due to the
aromatic ring vibrations and d(CH) vibrations of phenyl ring in
SBA-12/PAP sample were observed at 1600 cm1 and 692 cm1,
respectively. Finally, the band at 1556 cm1, observed in the spectrum of the sample SBA-12/AP and comprising bidentate carbonate
and NHCOO vibration [13,25,26], was shifted to a lower wavenumber in the spectrum of SBA-12/MAP, which may indicate formation of monodentate bicarbonate [21].
3.3. CO2 sorption
The CO2 uptake was measured by TGA. Fig. 8 shows carbon dioxide sorption on the amine-modied samples. The samples were rst
activated by heating to 110 oC and then cooled to 25 oC in inert gas.
During the sorption experiments the samples were purged with
10% CO2/N2 mixture (20 cm3/min). Upon introduction of the mixture a rapid weight gain was observed due to CO2 capture by amine
active sites of modied samples. The total amount of sorbed CO2
was 1.04 mmol/g for SBA-12/AP sample, 0.98 mmol/g for SBA-12/
MAP sample and 0.68 mmol/g for SBA-12/PAP sample. The mass
uptake was fast during the rst 5 min of exposure then the uptake
was slowing down until equilibrium was established after about
10 min of exposure.
Since under anhydrous conditions one mole of carbon dioxide
reacts with two moles of amine, we can calculate the theoretical
sorption capacity of modied materials using the results of elemental analysis (see Table 1). The maximal CO2 uptake calculated for
the sample SBA-12/AP represents 1.06 mmol/g. The maximal
sorption capacity calculated for the sample SBA-12/MAP is
1.07 mmol/g and for the sample SBA-12/PAP 0.78 mmol/g. The

Table 1
Results of elemental analysis and calculated amine surface densities in the prepared
amine-modied SBA-12 silica samples
Sample

Fig. 6. TG/DTA curves of SBA-12/AP (solid line), SBA-12/MAP (dashed line) and SBA12/PAP (dot-dashed line) during heating in air.

SBA-12/AP
SBA-12/MAP
SBA-12/PAP

Element content
C%

H%

N%

9.79
12.17
18.82

2.59
2.87
2.52

2.98
3.02
2.19

Amine
concentration
(mmol/g)

Amine surface density

NH2 groups (nm2)

2.13
2.16
1.56

0.94
0.97
0.70

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V. Zelenak et al. / Microporous and Mesoporous Materials 116 (2008) 358364

Fig. 8. Carbon dioxide sorption and carbon dioxide sorption rate on SBA-12/AP
(solid line), SBA-12/MAP (dashed line) and SBA-12/PAP (dot-dashed line).

Fig. 7. FT-IR spectra of the samples (a) SBA-12/AP, (b) SBA-12/MAP, and (c) SBA-12/
PAP.

efciency of the respective amines, expressed as the ratio g

sorbed CO2 mmol=g
nitrogen contentmmol=g

[13], decreased in the order SBA12-AP (g =

0.49) > SBA12-MAP (g = 0.45) > SBA12-PAP (g = 0.43). It is obvious,

that while for the sample SBA-12/AP the sorption capacity reached
theoretical value, for the SBA-12/MAP and SBA-12/PAP sample the
experimental uptake was lower. These differences may be explained when we consider Dankwerts mechanism [27] of reaction
between carbon dioxide and primary and secondary amines as well
as their basicity.
The overall reaction between CO2 and primary (AP) and secondary amines (MAP, PAP) is formation of carbamate. The reaction can
be expressed as

CO2 2R1 R2 NH ! R1 R2 NH
2 R 1 R 2 NCO2

where R1 = H for primary mines, R1, R2 = alkyl/aryl for secondary amines.

According to Dankwerts zwitterion mechanism the reaction involves a formation of a zwitterion intermediate, followed by the removal of a proton by a base [27].
CO2 R1 R2 NH ! R1 R2 NH CO
2

R1 R2 NH

CO
2

R1 R2 NH !

R1 R2 NH
2

R1 R2 NCO
2

The formation of carbamate requires break of amine NH bond

and trapping of proton by another amine group. Therefore the process depends on the ability of the amine to split/bind the proton. In
PAP molecule an aromatic ring connected to nitrogen atom makes
PAP less basic than AP or MAP ligands. This is due to the fact that
the lone pair of electrons on the nitrogen atom of PAP is delocalized into the aromatic p system. This stabilizes free PAP, and therefore makes the formation of a zwitterion intermediate from PAP
(see Dankwerts mechanism) more endothermic than the case of
AP or MAP, and thus less energetically favourable. Therefore the
stabilizing overlap in PAP, makes the lone pair less reactive and

PAP is a weaker base (pKb = 8.9) [28]. This property agrees with
the lower sorption capacity of carbon dioxide observed for PAP
modied material.
On the other hand, the electron donating methyl group is supposed to make MAP a stronger base than the primary amine
(AP). However the real situation is more complicated involving a
steric hindrance effect. The overall net result of the combination
of the electron donating and steric effects is that the secondary
amines are not in general stronger bases than primary amines
and therefore AP and MAP are of approximately equal basicity
pKb  4. Thus the small difference in carbon dioxide sorption
capacity observed for AP and MAP modied samples may be a consequence of steric hindrance and the lower accessibility of lone
electron pair of MAP, which may result in lower experimental carbon dioxide uptake observed by MAP modied silica in comparison
with AP modied silica.
These results were also conrmed in our recent work dealing
with measurement of isosteric adsorption heats of carbon dioxide
sorption on SBA-15 modied by AP, MAP and PAP [29]. With the
silica samples containing AP and MAP ligands (pKb  4) the enhanced values of qst at low surface coverage proved the strength
of the bond formed between CO2 molecule and amine group. On
the other hand, low values of qst observed for pure silica sample
and the sample containing PAP ligand indicated week interaction
of CO2 molecule with PAP or with pure silica surface [29].
It is to note, that we have performed the experiments in dry
conditions due to experimental set-up of our commercial apparatus. However the presence of water can further increase the sorption capacity since carbamate formed during the reaction of
primary and secondary amines with carbon dioxide can further react with CO2 and H2O to form bicarbonate


R1 R2 NCO
2 2H2 O CO2 ! R 1 R 2 NH2 2HCO3

or amine group can directly react with CO2 and H2O


R1 R2 NH H2 O CO2 ! R1 R2 NH
2 HCO3

In presence of water 1 mol of amine can capture 1 mol of carbon

dioxide. The study of inuence of water vapour on sorption capacity
was studied by several authors. Song et al. [30] showed that when
the feed concentration of moisture is lower than that of CO2, CO2
adsorption capacity increases rapidly with increasing moisture
concentration. When the feed concentration of moisture becomes
higher than that of CO2, CO2 adsorption capacity is not increased
by the excess of water [30]. Sayari et al. found out that presence
of moisture did not improve the performance of diethanolamine

V. Zelenak et al. / Microporous and Mesoporous Materials 116 (2008) 358364

impregnated MCM-41, on the other hand the moisture did not hinder it as was observed with zeolite 13X [18]. Moreover the DEA
impregnated MCM-41 showed good cyclic stability and maintained
its capacity for CO2 better than zeolite 13X tested at the same con-

Fig. 9. Cycles of carbon dioxide sorption/desorption studied by TG/DTA at 25 oC on

amine-modied silica (a) SBA-12/AP (b) SBA-12/MAP, (c) SBA-12/PAP. The 10% CO2/
N2 mixture (sorption) and argon (initial activation/desorption) were used during
the experiment.

363

ditions [18]. The study of Zheng et al showed that the presence of 2%

of water did not inuence the CO2 uptake in ethylenediamine modied SBA-15 [31]. SBA-15 silica modied by a series of amines was
studied by Yogo et al. The samples were shown to exhibit high
adsorption capacities for CO2 under moist as well as dry conditions
[13].
Desorption of carbon dioxide and regeneration of the sorbents
can be achieved by heating similarly to initial activation. However
the heating is energy consuming process and therefore we have
investigated the possibility of regeneration of the sorbents by
purge with inert gas without heating. The samples were submitted
to three adsorption/desorption cycles, each consisting of purge of
the samples with 10% CO2/N2 mixture (20 cm3/min) during adsorption step and purge the samples with argon (20 cm3/min) during
desorption/regeneration step.
The adsorption/desorption cycles are displayed in Fig. 9. These
curves show that the exposure of activated samples to 10% CO2/
N2 mixture leads to mass increase and evolution of heat as reected by TG and DTA curves. The subsequent purge with argon
led to desorption of carbon dioxide. The desorption process was
accompanied by consumption of heat evolved on adsorption. However as it can be seen from Fig. 9a, the complete desorption was not
achieved for sample SBA-12/AP. This is also supported by DTA results. More heat was evolved during the rst sorption process in
comparison with the subsequent two cycles (the rst exothermic
peak is strongest), indicating that the complete regeneration of
sorbent was not achieved during desorption process. For sample
SBA-12/MAP the situation was similar, even desorption took place
in the larger extend. On contrary, for the sample SBA-12/PAP complete desorption was observed in 10 min. Moreover, the DTA curve
showed neither exothermic nor endothermic peaks. As it was already mentioned, the sorption of carbon dioxide by amines takes
place mostly via the formation of carbamate species, with evolution/consumption of heat. Such behaviour was observed for the
samples grafted with AP and MAP ligands, but not for the PAP modied sample. The results could indicate that formation of carbamate in PAP modied material is limited and weaker interactions
(physisorption) may play a more important role during the sorption of carbon dioxide by SBA-12/PAP material, leading to faster
desorption and regeneration of the sorbent.
Since the adsorption/desorption studies were performed using
10% CO2/N2 gas mixture, it was of interest to study extent of coadsorption of carbon dioxide and nitrogen on the materials. There-

Fig. 10. Cycles of carbon dioxide sorption/desorption studied by TG/DTA at 25 oC

over SBA-12/AP sample. The pure CO2 (sorption) and nitrogen (initial activation/
desorption) were used during the experiment.

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V. Zelenak et al. / Microporous and Mesoporous Materials 116 (2008) 358364

fore sorption/desorption runs were repeated with pure carbon

dioxide (99.999%) used during the sorption step and pure nitrogen
used as an inert gas during the regeneration (desorption) step.
Fig. 10 shows sorption/desorption cycles of carbon dioxide sorption over SBA-12/AP sample.
From Fig. 10 it is obvious, that with pure carbon dioxide the
similar uptake was observed during the experiment like in the
study performed with 10% CO2/N2 gas mixture in adsorption step
and argon used in the regeneration step (Fig. 9a). This indicates
that no signicant co-adsorption occurred, which is in agreement
with the results of other authors showing that N2 sorption on functionalized silica was negligible and amine modied silicas displayed high CO2/N2 selectivity [17,19].
4. Conclusions
In the present study SBA-12 mesoporous silica modied by different amines was tested as solid CO2 sorbent. Grafting of the surface of SBA-12 silica with amine functionalities resulted in
different base strengths of the surface, which played an important
role in the chemical xation of carbon dioxide. The results have
shown that higher basicity of amino ligand increases efciency of
sorbents with respect to CO2. On the other hand, the regeneration
was faster for the sorbent containing active sites of lower basicity.
The efciency of amine-modied materials decreased in the order
SBA-12/AP > SBA-12/MAP > SBA-12/PAP. The maximal observed
sorption capacity was comparable with other monoamine modied mesoporous sorbents. The sorption/desorption cycles showed,
that the materials displayed high CO2/N2 selectivity and could be
used without signicant loss of CO2 capture capacity.
Acknowledgments
This work was supported by European Community STREP project DeSANNS (No. FP6-SES6-020133)), the Slovak Research and
Development Agency under the Contract No. RPEU-0027-06
(OrNaMat), MVTS6 and VEGA (1/0119/08) Project of Ministry of
Education of Slovak Republic. The TEM micrograph measurements
were supported by the Project 1M4531477201of Ministry of Youth

and Sports of the Czech Republic. The support is gratefully

acknowledged.
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