Journal of Industrial and Engineering Chemistry 17 (2011) 628632

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Journal of Industrial and Engineering Chemistry

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

Synthesis of copper exchanged heteropolyacids supported on MCM-48 and its

application for CO2 adsorption
Margandan Bhagiyalakshmi, Pushparaj Hemalatha, Mani Ganesh, Mei Mei Peng, Hyun Tae Jang *
Chemical Engineering Department, Hanseo University, Seosan 360-706, South Korea

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

Article history: Copper-encapsulated heteropolyacid-impregnated mesoporous MCM-48 (Cu-HPA-MCM-48) with

Received 8 September 2010 copper in a reduced state was synthesized, and the CO2 adsorption capacity was monitored. The
Accepted 17 November 2010 synthesized material was characterized by XRD, N2 adsorptiondesorption, FT-IR, DSC, CO2-TPD and XPS.
Available online 13 May 2011
The low angle X-ray diffraction pattern of the Cu-HPA-MCM-48 demonstrates the encapsulation of
copper inside the pore by the disappearance of higher-order peaks. This result is further supported by the
Keywords: presence of Cu2p3 and W4f peaks in XPS. The CO2 adsorption capacity of Cu-HPA-MCM-48 was 70 mg/g at
MCM-48
25 8C. The energy of desorption and the heat of the reaction (DHr) were 21.2 kJ/mol and 490 Btu/lb,
HPA
Copper oxide
respectively, as determined by CO2-TPD and DSC. As the DHr value of Cu-HPA-MCM-48 approaches the
Encapsulation CO2 benchmark value (580 Btu/lb), the catalyst exhibited improved CO2 capturing capacity.
CO2 adsorption 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction Recently, the electrocatalytic CO2 capture was investigated on a

Elevation in greenhouse gas level results in the anthropogenic
global warming. Extensive efforts has been devoted to reducing
greenhouse gas emissions, including using CO2 capture and storage
with coal power plant [1,2]. Solid sorbent adsorption is considered
as a potential option for the CO2 capture process [3]. One key
component in the development of these systems is obvious that
the sorbent must have good CO2 adsorption capacity, chemical and
mechanical stability for long periods of operation at repeated
cycles [4]. Towards this goal, metal oxides and mixed metal oxides
[57], high surface area porous materials such as zeolites [811],
carbon [12], metal-organic frameworks (MOFs) [1315], organo-
silica and surface-modied silica [1618] are currently studied. In
large-scale CO2 capture, several basic metal oxides demonstrated
high CO2 adsorption by chemical reactions with CO2 at elevated
temperatures: hence they suffer severe energy penalties, at high
desorption temperatures [3,1921].
Although alkali and alkaline-earth metal oxides such as CaO,
MgO, and K2O have been extensively investigated for CO2 capture
[22,23], it should be noted that many other metal oxides also
display CO2 adsorption properties under specic conditions.
Copper oxides also show excellent CO2 adsorption capacity [24
26]. In addition to copper oxide, copper complexes have been
shown to aid transformation of the CO2 to carbonate salt [27,28].
* Corresponding author. Tel.: +82 41 660 1423; fax: +82 41 688 1343.
E-mail address: htjang@hanseo.ac.kr (H.T. Jang).
copper complex in which copper in the reduced state spontane-
ously capture CO2 from the air and reductively coupled CO2 to form
a copper (II) complex [29]. This type of copper in a reduced state
can be observed in copper exchanged heteropolyacids. The
reported copper-exchanged heteropolyacid (Cu-HPA) is an ef-
cient candidate for several organic transformations [30]. The
afnity of CO2 for copper in a reduced state led us to use the Cu-
HPA complex for CO2 capture. Among the various HPA structural
classes, the commercially available Keggin-type [31] phospho-
tungstic acid was chosen for forming Cu-HPA complex.
Furthermore, recent consensus is that dispersion of metal
complexes over mesoporous silicas signicantly affects the property
of the metal complexes [32,33]. Most of the studies of surface
functionalization on mesoporous materials have focused on MCM-
41 silica, which has one-dimensional pore channel structure prone
to diffusion limitations and pore blockage [34]. Since, MCM-48
possesses three-dimensional interconnected cubic pore structure it
has drawn much attention as a potential support than MCM-41. Few
reports are available on CO2 adsorption over modied MCM-48. For
instance, Huang and Yang [35] studied an amine-grafted MCM-48
and reported that the amount of CO2 adsorbed reached 98.2 mg/g of
adsorbent at 1 atm and 25 8C. Kim et al. [36] studied CO2 adsorption
over various amines functionalized MCM-48 and reported
0.8 mmol g1 of CO2 adsorption for 3-aminopropyltriethoxysilane.
Gargiulo et al. [37] reported 6 wt% of CO2 adsorption on 50% PEI
loaded MCM-48. To the best of our knowledge, no reports are
available on metal oxide or metal complexes impregnated MCM-48
for CO2 adsorption. Consequently, we attempted to encapsulate the

1226-086X/$ see front matter 2011 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2011.05.010
 M. Bhagiyalakshmi et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 628632
Cu-HPA complexes over the mesoporous MCM-48 for CO2 adsorp-
tion studies. The MCM-48 possess large surface area (1000 m2/g),
pore size and uniform pore distribution, which makes them an
excellent support for the heteropolyacids (HPAs) [38]. Hence, the
feasibility of encapsulation of Cu-HPA complexes inside the MCM-
48 also plays a key role in enhancing the CO2 adsorption capacity of
Cu-HPA-MCM-48. The maximum CO2 adsorption capacity of Cu-
HPA-encapsulated, mesoporous MCM-48 is 70 mg/g at 25 8C.
Finally, the Cu-HPA-MCM-48 also is a recyclable, thermally stable
and green solvent for CO2 capture.
2. Experimental
2.1. Materials
Polyoxyethylene (23) lauryl ether (PLE), phosphotungstic acid
and Cu(SO4)5H2O were purchased from Aldrich and used without
further purication. Rice husk obtained from a local farm was
milled and heated to 700 8C for 24 h to obtain RHA. RHSSS was
extracted from RHA (3.8 g) by reuxing with 2 M NaOH in 38 ml
H2O at 70 8C for 24 h as per our previous report [39].
2.2. Synthesis of Cu-HPA impregnated mesoporous MCM-48
The experimental details pertaining to the synthesis of MCM-48
are described elsewhere [39]. The Cu-HPA complex was prepared
according to the reported procedure [30]. Briey, 0.18 g of barium
hydroxide was added (to neutralize the three protons) to the
aqueous solution containing 2.0 g of H3PW12O40 in 5 mL distilled
water. Thereafter, 0.16 g of CuSO45H2O was added to replace Ba
with Cu by eliminating the Ba as BaSO4. The Cu1.5PW12O40 salt in
solution was recovered by centrifuging. The mesoporous MCM-48
was wetted with the centrifugate. The slurry was stirred for 1 h,
dried under reduced pressure to obtain Cu-HPA-MCM-48. Finally,
the catalyst mass was dried at 120 8C for 12 h in an oven and calcined
at 300 8C for 2 h.
2.3. Characterization
Powder X-ray diffraction (XRD) patterns were recorded using
a Rigaku Miniex diffractometer with Cu-Ka radiation
(l = 0.154 nm). The diffraction data were recorded in the 2u
range of 0.558 at 0.028 step size and a 1 s step time. The
chemical compositions were measured by X-ray uorescence
(XRF, Philips PW2400). The nitrogen adsorptiondesorption
isotherms were measured at 196 8C on a Micromeritics ASAP
2010 volumetric adsorption analyzer. Prior to each adsorption
measurement the samples were evacuated at 150 8C under
vacuum (p < 105 mbar) in the degas port. The specic surface
area, SBET was determined from the linear part of the BET
equation, and the pore volume was calculated using a BET plot
based on the amount of nitrogen gas adsorbed at the last
adsorption point (P/P0 = 0.95) and the pore size distribution
using the BarrettJoynerHalenda (BJH) method. Fourier trans-
form infrared (FTIR) spectra of the samples were recorded at
room temperature on a Nicolet 6700 spectrometer equipped
with an attenuated total reection (ATR) cell. Each sample was
scanned 20 times at 4 cm1 resolution over the range 4000
400 cm1. X-ray photoelectron spectroscopy (XPS) was per-
formed on a Thermo Multilab 2000, using Monochrome Al Ka as
the excitation source. Scanning Electron Microscopy (SEM)
images show the morphologies of the samples after gold coating
obtained by a FEI Quanta 200 instrument operating at 30 keV
and equipped with an Energy dispersive X-ray spectroscopy
(EDS).
629
2.4. CO2-TPD
The temperature-programmed desorption (TPD) of CO2 was
performed on a BELCAT-M catalyst analyzer. The sample cell was
loaded with approximately 200 mg of the Cu-HPA-MCM-48 and
heated to 200 8C for 1 h under helium ow (80 ml/min). After it
was cooled to 25 8C, CO2 (diluted in He gas) (30 ml/min) was
introduced to the sample cell for CO2 adsorption for 60 min.
Afterwards, the TPD experiment was conducted from 25 to 500 8C
with a temperature ramp of 10.6, 15.8 and 20.8 8C/min by purging
helium (80 ml/min).
2.5. Differential scanning calorimetry (DSC)
A thermal cycle for Cu-HPA-MCM-48 was recorded using a
Scinco DSC N 650. Approximately 10 mg of sample was heated at
5 8C/min from 20 to 150 8C in dry helium, holding the sample
isothermally at 200 8C for 60 min for pre-activation. Then, the
sample was cooled from 200 to 25 8C at 5 8C/min and held
isothermally at the reaction temperature 25 8C for 60 min, and the
purge gas was switched from dry helium to CO2 diluted in He. The
recorded heat ow exhibits a noticeable exothermic peak as the
purge gas changed. The plot of resultant heat ux versus
temperature or time directly yields the heat of reaction for the
sample. The above experiments were repeated three times and the
average value is taken as heat of the reaction (DHr).
2.6. CO2 adsorption
CO2 adsorptiondesorption measurements for Cu-HPA-MCM-
48 were performed using Thermo Gravimetric Analyzer. A sample
weight of approximately 10 mg was loaded into an alumina sample
pan in a TG unit (SCINCO thermal gravimeter N-1000) and tested
for CO2 adsorptiondesorption performance. The initial activation
of the samples was carried out at 300 8C for 1 h in a nitrogen
atmosphere. Then adsorption run was conducted using high purity
CO2 (99.999%) gas, and the desorption run was conducted in N2
ow. The adsorption runs were conducted at 25, 50 and 75 8C
under atmospheric conditions, and desorption was determined at
200 8C. Both the gases, CO2 and N2 were passed through an
automatic valve, assisted with a timer for continuous adsorption
and desorption proles.
3. Results and discussion
3.1. Characterization
XRF results illustrated that MCM-48 obtained from rice husk
sodium silicate contains 99% SiO2 and cations such as Ca 2+, Mg 2+,
A13+ and Fe 3+ are present in traces amount (Table 1). Small-angle
powder X-ray diffraction patterns of MCM-48 and Cu-HPA-MCM-
48 are depicted in Fig. 1. The XRD pattern of MCM-48 shows an
intense peak below 2u = 38 corresponding to (2 1 1) and (2 2 0)
reections and a diffuse pattern in the region 348 (2u), which is
attributed to (4 2 0) and (3 3 2) reections [36], indicating la 3d
bicontinuous cubic phase for MCM-48. The Cu-HPA-MCM-48
shows a decrease in the intensities of (2 1 1) and (2 2 0) reections
and disappearance of higher order peaks due to the pore lling of
the mesoporous MCM-48 by the Cu-HPA complex. Furthermore,
the wide-angle patterns (inset in Fig. 1) are very clean, and all
diffraction peaks can be well indexed to the cubic Cu2O (JCPDS No.
78-2076) structure [40].
N2 adsorptiondesorption isotherms of MCM-48 and Cu-HPA-
MCM-48 are depicted in Fig. 2. Both MCM-48 and Cu-HPA-MCM-
48 shows a type IV, H1 hysteresis loop, and a sharp increase
between partial pressures 0.2 and 0.4 during adsorption and
630 [(Fig._3)TD$IG]
M. Bhagiyalakshmi et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 628632

Table 1 (c)
Chemical composition of MCM-48 from XRF.

Metal oxides wt.%

SiO2 99.52

Transmittance (%)
Al2O3 0.08
Fe2O3 0.08
CaO 0.09 (b)
MgO 0.05
K2O 0.09
Na2O 0.09 (a)
TiO2
MnO
P2O5

[(Fig._1)TD$IG]

4000 3500 3000 2500 2000 1500 1000

-1
Wavenumber (cm )

[(Fig._4)TD$IG] Fig. 3. FT-IR spectra of (a) MCM-48, (b) HPA, and (c) Cu-HPA-MCM-48.

O1s

Counts/s

Cu2p3

C1s
Si2p W4f
Fig. 1. XRD patterns of (a) MCM-48 and (b) Cu-HPA-MCM-48 (inset is wide angle
XRD patterns of Cu-HPA-MCM-48).

desorption indicating the capillary condensation of N2 in

mesopore. The surface area, total pore volume and average pore
diameter of MCM-48 is 1124.8 m2/g, 0.98 cm3/g and 3.89 nm,
respectively and of Cu-HPA-MCM-48 is 600.1 m2/g, 0.98 cm3/g and
3.89 nm, respectively. The specic surface area and pore size
distribution decreases after impregnation of the Cu-HPA complex
inside MCM-48, which apparently reveals the trapping of a Cu-HPA
complex inside the pores of MCM-48.
FT-IR spectra of MCM-48, HPA and Cu-HPA-MCM-48 are
depicted in Fig. 3. A broad band due to asymmetric stretching of
OH vibrations of silanols and water were observed at 3443 cm1
for MCM-48. The vibration bands due to HPA are observed at 1165,
[(Fig._2)TD$IG]1082 and 1021 cm1 for PO stretching, 940 and 913 cm1 for W
Volume of N2 adsorbed (cm3 /g)
1100 1000 900 800 700 600 500 400 300 200 100 0
Binding Energy (eV)
Fig. 4. XPS spectrum of Cu-HPA-MCM-48.
OW stretching, 788 cm1 for W5 5O stretching, and 573 cm1 for
PO bending (Fig. 3b). Cu-HPA-MCM-48 displays combined bands
due to bending vibration of SiOH in pure MCM-48 (in the range of
10501200 cm1) [36] and three PO stretching peaks in the HPA.
The XPS spectrum of Cu-HPA-MCM-48 was shown in Fig. 4. It
can be seen that the binding energy of Cu2p3 and W 4f in Cu-HPA-
MCM-48 are 932.5 and 36.83 eV, respectively [41], which indicates
that encapsulation of Cu-HPA complex inside the MCM-48 did not
affect the coordination environment of Cu (I) ions.

The morphology of MCM-48 and Cu-HPA-MCM-48 was

obtained on SEM. Fig. 5a shows SEM images of MCM-48
(a) demonstrating ne, spherical particles of 100200 nm in diameter,
which are similar to previous report [42]. While the SEM images of
Cu-HPA-MCM-48 (Fig. 5b) shows dispersion of the Cu-HPA
complex clusters over MCM-48. The EDS results (not shown)
conrm the presence of the Cu ion in Cu-HPA-MCM-48.
(b)
3.2. Thermal stability of Cu-HPA-MCM-48 by CO2-TPD

The thermal stability of CO2 sorbents is crucial in practical

applications as the CO2 adsorption and separation techniques
0 0.2 0.4 0.6 0.8 1 involve temperature swing adsorption. To determine the thermal
Relative pressure P/P0 stability of the synthesized Cu-HPA-MCM-48, multiple cycles of
adsorption at 25 8C and TPD were performed up to 600 8C. Fig. 6
Fig. 2. N2 adsorptiondesorption isotherms of (a) MCM-48 and (b) Cu-HPA-MCM- shows three-cycle TPD proles of CO2 on Cu-HPA-MCM-48. The
48.
second and third-run TPD proles were almost identical to the
[(Fig._5)TD$IG] M. Bhagiyalakshmi et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 628632 631

Fig. 5. SEM images of (a) MCM-48 and (b) Cu-HPA-MCM-48.

[(Fig._6)TD$IG]
is signicantly higher than that of HPA-MCM-48 (25 mg/g) and
pure MCM-48 (20 mg/g). This CO2 adsorption capacity is nearly
equal to that of previously reported Cu on porous carbon [24]. The
TCD Signal (a.u.)

basic feature of copper oxide present in Cu-HPA-MCM-48 is similar

(c)
(b)
(a)
200 300 400 500
Temperature (C)
Fig. 6. CO2-TPD proles of Cu-HPA-MCM-48 (a) rst, (b) second and (c) third run.
rst-run, indicating the high thermal stability of Cu-HPA-MCM-48
and its recyclability. The small peak at 150 8C corresponds to
weakly adsorbed CO2 while the broad peak at 250 8C represents
desorption of the strongly chemisorbed CO2 [43].
3.3. CO2 adsorption
Fig. 7 shows CO2 adsorption/desorption proles of Cu-HPA-
MCM-48 carried out at 25, 50 and 75 8C and the results are given in
Table 1. CO2 adsorption/desorption proles illustrates the initial
weight loss of approximately 5 wt% after preliminary activation at
300 8C in N2 atmosphere is due to loss of moisture content and
physisorbed CO2 on exposure to atmosphere. The maximum CO2
[(Fig._7)TD$IG]
adsorption capacity of Cu-HPA-MCM-48 is 70 mg/g at 25 8C, which
Fig. 7. CO2 adsorption (at 25, 50 and 75 8C) and desorption (at 300 8C) prole of
Cu-HPA-MCM-48.
to that of Cu2O in porous carbon; they are electron acceptors [24],
and consequently enhancing the CO2 adsorption capacity. The
acidbase interaction between copper oxide in Cu-HPA-MCM-48
and CO2 is reversible and a strong chemical bond. Previous reports
on adsorption of CO2 over Cu surface, by the DFT calculations
revealed that the adsorption capacity follows the trend Cu
(1 1 0) > Cu (1 0 0) > Cu (1 1 1) [44,45]. Therefore, it is noteworthy
to mention that the Cu in a reduced state in Cu-HPA-MCM-48 also
possesses a Cu (1 1 0) species, which is also evidenced from wide
angle XRD, contributes to the high CO2 adsorption capacity of Cu-
600
HPA-MCM-48. The effect of temperature on CO2 adsorption at 50
and 75 8C shows a decrease in the adsorption capacity, which
might be due to the increased kinetic energy of CO2 molecules,
hence they do not interact with the active Cu2O molecule.
The energy of desorption (Ed) was also calculated from CO2-TPD
by varying the heating rate (b = 283.6, 288.8, 296.8 K min1), using
the following equation:
 2  
T Ed E A0
log P log d (1)
b 2:303RT P RC
TP represents the desorption peak temperature (K), b the heating
rate (K min1), Ed the energy of desorption (kJ/mol), A0 the quantity
adsorbed (mmol g1), and C a constant (related to desorption rate).
Ed was calculated to be 21.2 kJ/mol from the slope by plotting
logTP2 =b vs. 1/TP which is in agreement with that of the Ed value
(18.0 kJ/mol) for CO2 adsorption on the Cu (1 1 0) surface [44].
Furthermore, heat of reaction (DHr) was calculated from DSC. A
maximum benchmark value of DHr of CO2 sorbent is 580 Btu/lb.
[46]. The DHr value of Cu-HPA-MCM-48 is 490 Btu/lb (50.12 kJ/
mol) from DSC that meets the energy requirements of a CO2
sorbent.
The reusability and reproducibility of Cu-HPA-MCM-48 were
conrmed by 20 consecutive CO2 adsorption (25 8C)/desorption
(300 8C) runs (gure not shown). There was no signicant change
in adsorption capacity. The XRD and IR results of the Cu-HPA-
MCM-48 after 20 cycles are similar to that of original Cu-HPA-
MCM-48 (gure not shown). In addition, the selectivity of Cu-HPA-
MCM-48 was studied by conducting the CO2 adsorption/desorp-
tion experiments with 15.21% CO2 in N2 and pure carbon dioxide
(99%) feed gas, as reported previously [39]. The absence of any
signicant change in adsorption capacity (Table 2) illustrates no
co-adsorption of N2 and high CO2 selectivity of Cu-HPA-MCM-48.
Furthermore, the inuence of desorption temperature on CO2
adsorption over Cu-HPA-MCM-48 at 350, 400 and 450 8C was
632 M. Bhagiyalakshmi et al. / Journal of Industrial and Engineering Chemistry 17 (2011) 628632
Table 2
The effect of adsorption temperature, desorption temperature, and CO2 concentration on CO2 adsorption on Cu-HPA-MCM-48.
CO2 adsorption temperature (8C) Temperature of N2 purging (8C)
25 300
50 300
75 300
25 300
25 300
25 350
25 400
25 450
presented in Table 2. The CO2 adsorption capacity at 25 8C and
desorption at 350, 400 and 450 8C were similar, which substanti-
ated that the CO2 adsorption over Cu-HPA-MCM-48 was not
physisorption.
The choice of oxides in the chemical looping combustion of fuel
is restricted, because it requires an oxide, which is exothermic
during reduction to balance the endothermic gasication reactions
[47]. This Cu-HPA complex contains such oxides, which can
withstand high temperatures at which gasication rates are
signicant. Hence, we are currently expanding the study for
chemical looping combustion with this Cu-HPA-MCM-48.
4. Conclusions
The Cu-HPA-MCM-48 material with copper in a reduced state
was synthesized, and investigated for CO2 adsorption. The
mesophase of Cu-HPA-MCM-48 was veried by XRD and N2
adsorption/desorption isotherms. The XPS and SEM-EDS results
revealed the presence of Cu2O particles in Cu-HPA-MCM-48. The
maximum adsorption capacity at 25 8C is 70 mg/g. This complete
desorption of adsorbed CO2 at 300 8C supports the potential of Cu-
HPA-MCM-48 as a low temperature swing sorbent. The chemi-
sorption of CO2 on the Cu-HPA-MCM-48 was conrmed by the
CO2-TPD results. The energy of desorption from the CO2-TPD and
the heat of reaction from DSC is 21.2 kJ/mol and 490 Btu/lb,
respectively. The above results further supported the chemisorp-
tion of CO2 over Cu-HPA-MCM-48. The heat of reaction from DSC
shows that the Cu-HPA-MCM-48 meets the energy requirement for
of a CO2 sorbent. Hence, the synthesized Cu-HPA-MCM-48 is
reusable, selective, thermally stable and a promising nominee for
CO2 capture.
Acknowledgements
This study was supported by a grant (code CD3-201) from
Carbon Dioxide Reduction & Sequestration Research Center, one of
the 21st Century Frontier funded by the Ministry of Science and
Technology of Korean Government.
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