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CERAMICS
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Ceramics International 40 (2014) 75837587

www.elsevier.com/locate/ceramint

Short communication

Amine-grafted zeolites-mesoporous ceramics: Synthesis

and adsorption characteristics
Daisy Aruldossa, Rahul Saigoankerb, Jerome Das Savarimuthua, Jagannathan R.c,n
a
Department of Physics, Loyola College, Chennai 600034, India
Department of Metallurgical and Materials Engineering, National Institute of Technology, Suratkal 575025, India
c
Functional Materials Division, CECRI-CSIR, Karaikudi 630006, India

Received 1 October 2013; received in revised form 20 November 2013; accepted 22 November 2013
Available online 11 December 2013

Abstract
Through a facile synthesis method, amine-grafted zeolites-based mesoporous ceramics as effective adsorbents for green-house gases, CO2 in
particular, have been synthesized. Analyses on these mesoporous samples, using SAXD and SEM studies, indicate minor modication in the
chemical texture of the ceramics. The chemisorbed gaseous species have been analyzed using BET and FTIR spectra. Grafting of the mesoporous
solid with less saturated amine species, such as, TETA and DETA, enhances the adsorption of the green-house gas CO2 by about 40% in
comparison to the samples prepared through grafting with more saturated alcohol-based amine group TEA.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Ceramics; Mesoporous solids; Adsorption; Green-house gases

1. Introduction
Environmental scientists are much concerned about the
ever-increasing emissions of green-house gases in general,
and CO2 gas in particular, which will eventually pollute the
atmosphere. Hence, they are exploring ways to have control
over such emissions through several methods including the
introduction of effective adsorbents [1]. There have been
sustained research and development (R & D) interests on
feasible methods for the synthesis of adsorbents which can
alleviate atmospheric pollution by mitigating the greenhouse
effect and global warming [2]. The synthesis process for the
ceramic-adsorbents based on solgel combustion/thermolyis,
the post-combustion technique, poses design challenges owing
to the low partial pressure of CO2 ue gases and the relatively
high temperature of the same. Still, it is benecial because it
Abbreviations: BET, Brunauer,Emmett, Teller method; SAXD, Small angle
X-ray diffraction; SEM, Scanning electron microscopy; FTIR, Fourier transform infrared spectra; DETA, Diethylenetriamine; TETA, Triethyl-tetramine;
TEA, Tri ethanolamine; CCS, Carbon capture and sequestration
n
Corresponding author. Tel.: 91 9487 167 780; fax: 91 4565 227 713.
E-mail address: jags57_99@yahoo.com (Jagannathan R.).

utilizes proven chemical absorption methods. Of the several

technologies known for the CO2 capture and storage or
sequestration (CCS), post-combustion capture is more benecial as this can be used without fundamental changes [3]. It
should be borne in mind that solid adsorbents over liquid
amines could effectively alleviate energy penalties, environmental and atmospheric pollution from these gases. Zeolites, in
particular, have shown signicant CO2 adsorption capacities at
room temperatures or lower temperatures (
25 1C) [4] providing selectivity which is 510 times greater than carbonaceous materials. This serves as the motivation for the present
work focusing on zeolites based absorbents for greenhouse
gases. With this objective in mind, in this work different
amines have been grafted into the mesoporous zeolite medium
and their CO2 adsorption capacities have been analyzed.
However, to nd a place for real applications, this system
has still a long way to go after taking care of sizespace
limitations, recyclability, and so on. To start, this new system
of materials can be tried in small devices, such as, reextinguishers, fume-exhaust chamber etc.
The pristine ZSM-5 (abbreviation for Zeolite Socony Mobil-5)
belongs to the family of aluminosilicate zeolites with a pentasil

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.11.111

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A. Daisy et al. / Ceramics International 40 (2014) 75837587

structure adsorbing 0.38 mmol/g [5]. Surface modied porous

silica materials, such as, SBA-15 (Santa Barbara Acids), MCM41 (Mobil composition of matter) and zeolites can be efciently
employed to capture CO2 gas at moderate temperatures. High
surface area and uniform porosity are the two synergetic effects
determining the adsorption capacity of any solid adsorbent [5].
The apparent pore size and the surface area decrease while
incorporating the amine into the parent material leading to the
increase in adsorption capacity.
2. Materials synthesis and characterization
Samples of template-free ZSM-5 with molar ratio SiO2/
Al2O3 (silica to alumina ratio) of 50 were synthesized through
a conventional solid state method [6]. ZSM-5 was prepared by
dissolving 4.0 g sodium hydroxide and 1.64 g sodium aluminate in 135 g of distilled water in a beaker. The above mixture
was thoroughly stirred using a mechanical stirrer until a clear
solution was obtained and 81 g of colloidal silica (37 wt%)
was gradually added to the above solution under vigorous
stirring. The molar composition of the resulting gel was
12Na20:100SiO2:Al2O3:2500H20. Before transferring into a
Teon-lined stainless steel autoclave, the synthesized solution
was allowed to remain for 24 h at room temperature. Subsequently, it was hydrothermally treated for 24 h in an oven at a
temperature of 180 1C. After the hydrothermal treatment, the
products were recovered, thoroughly washed with distilled
water until pH reduced to neutral (
7), and dried at room
temperature. The prepared product was characterized using
polycrystalline X-ray diffraction and BET analysis for chemical phase purity and surface area determination, respectively.
Furthermore, the chemical purity of the synthesized sample(s)
was ascertained using small angle X-ray diffraction (SAXD)
proles of the pristine and the amine functionalized ZSM-5
samples as shown in Fig. 1. From this, we have that templatefree ZSM-5 powders, which can be matched with ICDD
standard le #00-044-0003. The XRD pattern shows peaks
in the ranges of 2 791 and 2351 corresponding to peaks
characterizing ZSM-5 zeolite phase. Nevertheless, upon incorporating the amines into the matrix, a notable decrease in the
diffraction peak intensities is observed (Fig. 1). Furthermore,
the synthesis of ZSM-5 was tried with different molar ratios of
SiO2/Al2O3 in the range of 50100. In all these trials, the
optimum molar ratio of SiO2/Al2O3 of 50 yielded good results.
In the preparation of the SBA-15 sample, the stock solution
was prepared [7] by dissolving 4.0 g pluronic acid (2.66 g
polyethylene glycol PEG) and (1.34 g polypropylene glycol) in
130 ml of distilled water in a beaker. The above mixture was
thoroughly stirred at 40 1C until a clear solution was obtained.
Then, into this mixture, 20 ml of 1 M HCl was added while
stirring continuously. Subsequently, clear solution silica was
added into it, followed by continuous stirring for 68 h at
40 1C. The molar composition of the resulting synthesis
solution mixture was 1SiO2:0.33Na2O:0.017(PPGPEG):
1.4HCl:95H2O. Before transferring to a Teon-lined stainless
steel autoclave, the above synthesis solution was maintained at
80 1C for 1224 h, and then, hydrothermally treated for 24 h in

Fig. 1. SAXD for template free ZSM5 with template, amine grafted ZSM5
after adsorption of CO2. (a) ICDD-00-044-0003, (b) ZSM5 with template,
(c) ZSM5 without template and (d) ZSM-TETA after adsorption.

an oven at a temperature of 120 1C. After the hydrothermal

treatment, the products were recovered, thoroughly washed
with distilled water, and dried at room temperature. The dried
powder was then calcined at 550 1C at a ramp rate of 1 1C/min
for 6 h.
Thus, the synthesized adsorbents, viz., ZSM-5 and SBA-15,
were modied with amines as functional groups through a wetimpregnation method [812]. For this purpose, ethanol/methanol was used as the solvent to allow the amine solution to
dissolve the mixture before adding to the sorbent. The amines
were selected based upon their boiling points. [1315]. The
amine-loadings were varied in the range of 2060 wt% (w/0).
Calculated quantities of the adsorbent(s) were dispersed in
ethanol/methanol and subjected to sonication for deagglomeration at 200 kV for 20 min, which was followed by
the addition of calculated amine solution [1619]. After this,
the resulting slurry was stirred magnetically for about half an
hour and dried at 70 1C for 24 h to remove the solvent and
used for further characterization as schematized in Fig. 2. The
presence of amine-functionalized groups and modication has
further been conrmed using FTIR spectroscopy.
3. Results and discussion:
3.1. Amine grafting and adsorption of CO2 in mesoporous
silica zeolite:
The FTIR spectrum of ZSM-5 zeolite nano-ceramics without any organic templates is shown in Fig. 3. From the infrared
spectrum, corresponding to the sample ZSM-5, we can observe

A. Daisy et al. / Ceramics International 40 (2014) 75837587

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Fig. 2. Flow chart for synthesis of amine grafted zeolite for CO2 capture application.
1.1

% transmittance

1.0

0.9

0.8

4000

3500

3000

2500

2000

1500

1000

500

-1

wave number(cm )

Fig. 3. FTIR transmission spectra for amine grafted zeolite and SBA solid
sorbents. bold arrows indicate modication in vibrational modes. (a)
ZSM5 TEA and (b) SBA15TETA.

intense absorption bands at wave-numbers 527, 781, 1025,

1210, 1445, and 3269 cm  1. The presence of an infrared band
at 527 cm  1 may correspond to the ve-membered ring of the

pentasil zeolite structure. Additional evidence for the nanosized zeolite is the asymmetric stretch vibration of TO bond
at 1210 cm  1 which can be assigned to external linkages
between tetrahedra formed by SiO4 and AlO4, these being
structure-sensitive IR band(s). The FTIR spectrum for TETAmodied ZSM-5, with a slight shift in the peak position with
no additional peak(s) characteristic of free amines, might
suggest the coordination of these amines with ZSM-5 sample.
Data, related to the BET surface area analysis, total pore
volume, and pore-width, are summarized in Table. 1. The BET
specic surface area of the synthesized ZSM-5 zeolite powder
sample was measured after degassing at 300 1C for 3 h. The
surface area was determined to be 373 m2/g, while the BET
surface-area for the modied SBA15 was observed to be
920 m2/g (Fig. 4). The amine incorporated ZSM-5 showed a
signicant decrease in the surface area of the ZSM-5. This may
suggest the inclusion of amine molecules into the pore
channels of ZSM-5 as the molecular sizes of the amines were
relatively low.
The morphology of the synthesized ZSM-5 zeolite ceramics
has been investigated using scanning electron microscopy
(SEM). From Fig. 5, depicting the particle morphology using
SEM, we can see that ZSM-5 zeolite crystals are found to be

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A. Daisy et al. / Ceramics International 40 (2014) 75837587

Table 1
Materials, CO2 adsorption data for ZSM5 and modied SBA15.
Solid sorbent

SAXD

CO2 adsorption

BET results

Particle size (nm) Surface area (m2/g) Total pore volume (cc/g) Average pore radius (A ) Support system Adsorption of CO2 (mg/g)
ZSM-5

76

Modied SBA-15 43

373

1.306  10  01

9.37975

920.4686

0.483760

36.087

TEA
DEA
DETA
TETA
DETA
TETA

47
48
55
60
88
210

zsm
3.0

1/[W(P0/P)-1]

2.5

2.0

1.5

1.0

0.5

0.0
0.05

0.10

0.15

0.20

0.25

0.30

Relative pressure(P/P0)

Fig. 6. CO2 adsorption capacity of modied SBA15 for three cycles.

Fig. 4. The BET surface area plot for zeolite solid sorbent which gives 373 m2/
g surface area.

Fig. 5. SEM micrograph image of the zeolite solid sorbent.

spherical, irregular, and benzene structured possibly because

smaller particles have a higher surface area. ZSM-5 zeolite
crystals are unique as they contain interconnected micropores
and mesopores inside each individual single crystal.

The adsorption capacity of the sorbents loaded with primary

amines is very low compared to the adsorption capacities of
the sorbents loaded with secondary and tertiary amines. The
highest adsorption capacity was achieved for the sorbent
loaded with 40 wt% of TETA. Fig. 6 shows the percentage
of CO2 adsorbed with respect to time for the sorbent loaded
with 40 wt% of TETA. It can be clearly seen that during the
initial period, all of the CO2 is adsorbed, as the sorbent is
highly active. The adsorption rate decreases with time as the
number of active sites are reduced. It is also observed that
about 90% of the CO2 is absorbed by the sorbent within the
rst 5 min of the exposure to CO2 gas/atmosphere.
Furthermore, adsorption studies were carried out at a
temperature range of 6575 1C, while desorption was carried
out at 100110 1C. It was observed that the adsorption
capacity was higher compared to the sorbent with ZSM-5 as
support.
From the foregoing results, it is reasonable to generalize that
these mesoporous ceramics, grafted with less saturated amines,
such as, DETA and TETA, show a pronounced tendency to
adsorb CO2 gas (
40% more) than with saturated alcoholbased TEA. Fortuitously, both stretching () and bending ()
modes of OSiO and (CO3)2  , also 1 and 2 modes of
(CO3)2  occurred and almost crowded in the same region of
7001100 cm  1 for both species [19]. Hence, suitable grafting
with a less saturated amine might facilitate better adsorption of

A. Daisy et al. / Ceramics International 40 (2014) 75837587

CO2 as the case is observed. Furthermore, loss in adsorption

capacity of these amine grafted mesoporus solid(s) is minimal,
suggesting that the sorbent is thermally stable and regenerable.
The sample ZSM-5 could be loaded with amine only upto
45 wt%. After this, further addition of amine leads to the
formation of a coat over the material leading to reduction in
adsorption capacity. However, SBA-15 could be loaded up to
75 wt%, resulting in an increased adsorption capacity. The
higher loading of mesoporous support can be explained in
terms of a larger pore volume present in the material
accommodating a higher amount of amine(s) when compared
to the microporous material. The thermal stability of the SBA15 grafted amine is better than the ZSM-5 grafted amine,
showing very little loss of adsorption capacity over multiple
cycles.
4. Conclusions
In this study, regenerable amine-grafted mesoporous zeolites
as adsorbents for greenhouse gases have been successfully
synthesized. This study has shown that TETA-modied SBA15 exhibits the highest CO2 adsorption capacity at 210 mg/g
sorbent while DETA modied ZSM-5 sample's adsorption was
the lowest at 88 mg/g sorbent. Consequently, SBA-15 is
thermally more stable and a better system for CO2 adsorption
than ZSM-5 in terms of adsorption capacity and cycle-stability.
This may be due to better bonding, low loss of amine and
higher fraction of amine loading for the microporous support
than for the mesoporous support. In any case, for transforming
these results into real application, one should also take into
consideration the cost-factor of the precursors involved.
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