Microporous and Mesoporous Materials 164 (2012) 3–8

Contents lists available at SciVerse ScienceDirect

Microporous and Mesoporous Materials

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

One-pot synthesis of mesoporous Cu–c-Al2O3 as bifunctional catalyst for direct

dimethyl ether synthesis
Heqing Jiang, Hans Bongard, Wolfgang Schmidt, Ferdi Schüth ⇑
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany

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

Article history: Mesoporous copper–alumina (Cu–Al2O3) with different copper contents was synthesized in a one-pot
Available online 23 August 2012 reaction via the evaporation-induced self-assembly of Pluronic P123 and the corresponding metal precur-
sors in ethanolic solution in the presence of nitric acid. Mesoporous Cu–Al2O3 calcined at 400 °C exhibits
Dedicated to Prof. Jens Weitkamp on the
occasion of his 70th birthday a large BET surface area of 265 m2/g and a pore volume of 0.48 cm3/g. XRD results indicate that the wall of
mesoporous Cu–Al2O3 calcined at 400 °C is amorphous, and that it is transformed to crystalline material
by further thermal treatment at 800 °C. Copper was formed as very small particles in the composite under
Keywords:
Evaporation-induced self-assembly 5% H2 flow at high temperature. Moreover, the mesoporous structure did not collapse after the sample
Mesoporous materials was reduced at 650 °C for 4 h, and the copper particles with sizes of around 6 nm were well distributed
Synthesis gas through the entire mesoporous c-Al2O3 network. Using the mesoporous Cu/c-Al2O3 as a bifunctional cat-
Cu/c-Al2O3 alyst for one-step dimethyl ether synthesis from synthesis gas, a CO conversion of 72% and a DME selec-
Dimethyl ether synthesis tivity of 69% were obtained at 50 bar and 310 °C.
Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction Compared to methanol dehydration (2), methanol synthesis (1)

In addition to being the building block for several industrially
important chemicals [1,2], dimethyl ether (DME) is exploited as a
sulfur-free alternative diesel fuel due to its low NOx emissions
and almost no particulate formation during combustion [3–5].
Moreover, it may also be used as a source of hydrogen for fuel cell
applications [6,7]. At present, DME is mainly produced from syn-
thesis gas by two possible approaches. One is a two-step method
including methanol synthesis from synthesis gas (1) over copper-
based catalysts [8–10] and the subsequent methanol dehydration
to DME (2) on a solid acid catalyst, such as gamma alumina (c-
Al2O3) [11,12] or different zeolites [13–15]. The other is the direct
synthesis of DME from synthesis gas in one step in the presence of
a bifunctional catalyst or physically mixed catalysts. Water formed
by methanol dehydration (2) will partly be consumed by the water
gas shift reaction (3). Thus, the overall reaction is described by Eq.
(4).
2CO þ 4H2
2CH3 OH ð1Þ
2CH3 OH
CH3 OCH3 þ H2 O ð2Þ
CO þ H2 O
H2 þ CO2 ð3Þ
3CO þ 3H2
CH3 OCH3 þ CO2 ð4Þ
⇑ Corresponding author. Tel.: +49 208 306 2373; fax: +49 208 306 2995.
E-mail address: schueth@mpi-muelheim.mpg.de (F. Schüth).
is more equilibrium-controlled. The equilibrium limitation of
methanol synthesis (1) can be overcome by coupling it with the
methanol dehydration step (2). In the single step process, the
formed methanol can be quickly consumed by the consecutive
methanol dehydration (2) if two types of active site are very close
to each other in the bifunctional catalyst system. To favor the cat-
alytic reaction, it is crucial to obtain a very fine distribution of two
types of active site in the composite catalyst. Previous studies
mostly focus on the physical mixture of the two types of catalysts,
improving the activity and lifetime [16,17]. Very recently, Yang
et al. reported a well-designed H–ZSM-5/Cu–ZnO–Al2O3 capsule
catalyst with core–shell structure, which exhibited a higher selec-
tivity for DME compared with the conventional hybrid catalyst
[18]. In this work, we explore a bifunctional catalyst with mesopor-
ous structure for one-step DME synthesis.
c-Al2O3 has been widely used as methanol dehydration catalyst
due to its moderate acidity, low price, and easy availability [11,12].
Recently, Yuan et al. reported a facile route to synthesize ordered
mesoporous c-Al2O3 by self-assembly of Pluronic P123 triblock
copolymer and alumina precursors in ethanolic solution [19]. Later,
this method was further extended to synthesize mesoporous alu-
mina-supported noble metals or metal oxides such as CeO2, NiO,
TiO2, Cr2O3, etc. [20–22]. Compared to the conventional wet
impregnation method, the mesoporous alumina supported metals
by one-pot method were reported to have high-quality meso-
structures that exhibit strong metal-support interactions and a
homogeneous distribution of active sites [23]. A bifunctional cata-

1387-1811/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2012.08.004
4 H. Jiang et al. / Microporous and Mesoporous Materials 164 (2012) 3–8
lyst for one-step DME synthesis can be obtained by loading copper
on the surface of c-Al2O3 using the conventional impregnation
method or the co-precipitation and deposition method reported
by Baek et al. [24]. In order to get a high dispersion of copper,
we therefore extended the one-pot method described above for
the synthesis of mesoporous c-Al2O3 supported copper (Cu/c-
Al2O3), and explored its application as bifunctional catalyst for
one-step DME synthesis from synthesis gas after reduction of the
copper species to result in a supported catalyst Cu/ c-Al2O3.
2. Experimental
2.1. Synthesis of mesoporous Cu–c-Al2O3
The mesoporous Cu–c-Al2O3 was prepared based on the evapo-
ration-induced self-assembly procedure using Pluronic P123 as a
structure directing agent, following the previous reports [19,21].
In a typical synthesis, 2.0 g of Pluronic P123 (EO20PO70EO20 from
BASF, Co.) was dissolved in 40 mL of ethanol, and the mixture
was stirred at 30 °C for 4 h. Then 3.2 mL of 65 wt.% nitric acid
(J.T. Baker) and the appropriate quantity of copper(II) nitrate trihy-
drate (99–104%, Sigma–Aldrich) and aluminum isopropoxide (98%,
Aldrich) were added into the above solution with vigorous stirring.
The total amount of metal species was kept constant (20 mmol),
and the molar ratio of copper to aluminum was adjusted accord-
ingly. The beaker (volume: 100 mL) containing the mixture was
covered with PE film and stirred at 30 °C for about 12 h. Then the
final solution was put into a drying oven and underwent the sol-
vent evaporation at 60 °C for two days. Calcination was carried
out by slowly increasing temperature from room temperature to
400 °C (1 °C/min ramping rate) and holding at 400 °C for 4 h under
air. The Cu–c-Al2O3 was obtained by further treating the above
sample at 800 °C for 4 h. The final samples were labeled in the gen-
eral form xCu–Al-T, starting with copper molar percentage (x), Cu
indicating copper, Al indicating aluminum, followed by calcination
temperature (T). For example, 5Cu–Al-800 refers to the mesopor-
ous aluminum oxides with 5% molar fraction of copper, which
was calcined at 800 °C for 4 h in air.
2.2. Characterization
Powder X-ray diffraction (XRD) measurements were performed
on a Stoe STADI P diffractometer operating in reflection mode with
Cu Ka radiation at room temperature from 0.7° to 5° (small angle)
and 20° to 80° (wide angle). Scanning transmission electron micro-
scope (STEM) images were taken on a Hitachi S-5500 microscope
with an EDS detector operating at an acceleration voltage of
30 kV. The samples were prepared on carbon-coated nickel grid.
Nitrogen adsorption–desorption isotherms were obtained on a
NOVA 4200e instrument at 196 °C. Prior to the measurements,
all samples were degassed under vacuum for around 12 h at
300 °C. The BET surface area was calculated from the data in a rel-
ative pressure range from 0.04 to 0.2. By using the Barrett–Joyner–
Halenda (BJH) model, the pore volumes and pore size distributions
were derived from the adsorption branches of isotherms.
Temperature-programmed reduction (TPR) was performed in a
homemade apparatus loaded with 100 mg of sample, using a gas
mixture of 5% H2 in nitrogen at a flow of 30 ml/min. The tempera-
ture was raised from room temperature to 650 °C with a heating
rate of 10 °C /min. The water produced during the reduction was
trapped on a 5A molecular sieve. The amount of hydrogen con-
sumed by the reduction was measured by a thermal conductivity
detector (TCD).
2.3. Catalytic synthesis of DME
Catalytic activity of mesoporous Cu/c-Al2O3 was evaluated in a
fixed bed stainless-steel reactor with an inner diameter of 6 mm. A
mixture of CO (6 ml/min), H2 (12 ml/min) and N2 (2 ml/min) was
sent to the top section of the reactor that acted as a pre-heater.
All gas flows were controlled by mass flow controllers (Brooks,
Model 5850), which were calibrated by using a soap bubble meter
before measurement. 1.0 g of catalyst (grain size 250–500 lm) was
loaded in the middle section of the reactor. The catalyst was re-
duced at 250 °C for 4 h in flowing 5% H2 in N2 prior to the catalytic
measurement. The catalytic reaction was conducted at a pressure
of 50 bar and temperatures from 280 to 325 °C. Before the first data
point was taken, the catalyst was equilibrated under reaction con-
ditions for 15 h, after this time typically a stationary state was
reached. Then the temperature was increased stepwise to assess
the performance of the catalysts at different temperature. Repro-
ducibility of the performance for different catalysts and experi-
ments was found to be highly satisfactory, with differences in
conversions amounting to less than 3%. The effluent gas, after
reducing its pressure by a back pressure regulator, was directly
sent to an on-line gas chromatograph (Agilent 7890). All gas lines
to the reactor and the gas chromatograph were heated to 160 °C
to avoid the possible condensation of water and methanol. The
gas chromatograph was equipped with two parallel channels to
two detectors: a thermal conductivity detector (TCD) and a flame
ionization detector (FID). The TCD channel was used with packed
columns (HayeSep Q and molecular sieve 5A) to separate and ana-
lyze CO, N2 and CO2, whereas the FID channel with a capillary col-
umn (HP-PLOT Q) was employed to analyze DME, methanol, and
possible hydrocarbons. The conversion of CO (XCO) is defined as
follows:
Fðtotal; inÞ  cðCO; inÞ  Fðtotal; outÞ  cðCO; outÞ
X co ¼  100%
Fðtotal; inÞ  cðCO; inÞ
The selectivities for DME (SDME) and CO2 (SCO2) are calculated
based on the number of carbon atoms in the feed and product
streams, as indicated by the following equations:
2  Fðtotal; outÞ  cðDME; outÞ
SDME ¼  100%
Fðtotal; inÞ  cðCO; inÞ  Fðtotal; outÞ  cðCO; outÞ
Fðtotal; outÞ  cðCO2 ; outÞ
SCO2 ¼  100%
Fðtotal; inÞ  cðCO; inÞ  Fðtotal; outÞ  cðCO; outÞ
where F (total, in) is the total flow rate of the mixing gases at the
inlet of the reactor, and F (total, out) represents the total flow rate
of the effluent gases, which was obtained by using N2 as an internal
standard. c (i, out) is the concentration of the corresponding gas at
the exit of the reactor, which was determined by the calibrated gas
chromatograph.
3. Results and discussion
Fig. 1 presents the small angle XRD patterns of samples with
different copper contents prepared by the one-pot method. The
samples 2Cu–Al-400 and 5Cu–Al-400 exhibit a very strong diffrac-
tion peak at 1.0° and one weak peak at around 1.7°, indicating the
presence of uniform mesoporosity, which could either be ordered
or worm-like. With further increasing copper content up to 15%,
the small angle reflection becomes less defined, until at 15% it is
not present any more. This indicates an increasing effect of the
introduction of copper into the alumina matrix on the formation
of the mesoporous structure. At a copper content of 15%, the order
of the pore system is obviously lost. The wide angle XRD pattern of
 H. Jiang et al. / Microporous and Mesoporous Materials 164 (2012) 3–8 5

Fig. 1. Small angle XRD patterns of mesoporous Cu–Al2O3 with different molar
fractions of copper and aluminum calcined at different temperatures.

the sample 5Cu–Al-400 (Fig. 2) indicates that the wall of the mes-
oporous Cu–Al2O3 is amorphous, which normally results in poor
hydrothermal stability. After further treating at 800 °C for 4 h,
the amorphous Cu–Al2O3 was transformed into crystalline Cu–c-
Al2O3. As shown in Fig. 2, the XRD pattern of 5Cu–Al-800 displays
three reflections at 37.5°, 45.8° and 66.9°, indicating the formation
of crystalline Cu–c-Al2O3 [19,25,26]. The absence of isolated cop-
per oxide or other copper-related compounds indicates that copper
was incorporated into the alumina matrix, thus leading to a fine
distribution of copper on the atomic level. It is noted that the good
mesoscopic order is still maintained after the treatment at 800 °C.
As shown in Fig. 1c, the peak at 1.0° is still present in the small an-
gle XRD pattern of 5Cu–Al-800, indicating the good thermal stabil-
ity of the mesoporous Cu–Al2O3.
The formation of mesoporous Cu–Al2O3 is also supported by Fig. 3. Nitrogen adsorption isotherms (top) and the corresponding pore size
distribution (bottom) for Cu–Al2O3 calcined at different temperatures.
nitrogen adsorption measurements. Fig. 3 shows the nitrogen
adsorption–desorption isotherms and the corresponding pore size
distribution for the samples treated at 400 and 800 °C. Both iso-
and the sample 5Cu–Al-800 has a BET surface area of 198 m2/g
therms are type IV with H1 hysteresis loops, indicating the forma-
and a pore volume of 0.38 cm3/g. The corresponding pore size dis-
tion of uniform mesopores. The sample 5Cu–Al-400 exhibits a large
tribution curves in Fig. 3 reveal a narrow pore size distribution cen-
BET surface area of 265 m2/g and a pore volume of 0.48 cm3/g. To
tered at around 8 nm for 5Cu–Al-400 and 6 nm for 5Cu–Al-800.
get the catalytically active component c-Al2O3 for methanol dehy-
The reduction of pore size is probably due to the shrinkage of the
dration, the treatment at higher temperature is necessary accord-
structure after the thermal treatment.
ing to the XRD studies. It can be seen from Fig. 3, that after
In the mesoporous Cu–Al2O3 catalyst system, copper after its
transforming the catalysts to crystalline Cu–c-Al2O3 by further
reduction is expected to work as active component for methanol
treatment at 800 °C, the mesoporous structure does not collapse,
synthesis and the crystalline c-Al2O3 matrix as an acid component
for methanol dehydration. According to previous TPR studies, the
reduction temperature of copper oxide under hydrogen is around
250 °C [27–29]. In this work, in order to obtain a homogeneous dis-
tribution, copper first was incorporated into the alumina matrix,
forming Cu–Al–O crystalline network that is normally reduced at
320–390 °C [29–31]. Fig. 4 presents the reduction profile of the
sample 5Cu–Al-800. The onset of reduction is around 170 °C and
a broad reduction peak centered at around 330 °C was observed
in the TPR patterns. The higher reduction temperature of the crys-
talline Cu–Al2O3 indicates that copper had really been incorporated
in the crystalline alumina network, which is in accordance with the
XRD results. Fig. 5 shows the XRD patterns of 5Cu–Al-800 before
and after reduction under 5% H2 flow at different temperatures
for 4 h. There is no obvious change in the XRD patterns of the sam-
ples reduced at 280 or 500 °C, and no reflections characteristic of
metallic copper particles were detected.
STEM was used to observe the morphology change of the sam-
ples before and after reduction. It was found that both ordered and
Fig. 2. Wide angle XRD patterns of Cu–Al2O3 calcined at different temperatures. worm-like mesoporous regions are present in the Cu–Al2O3 pre-
6 H. Jiang et al. / Microporous and Mesoporous Materials 164 (2012) 3–8
Fig. 4. TPR profile of the sample 5Cu–Al-800.
Fig. 5. XRD patterns of 5Cu–Al-800 before (a) and after reduction under 5% H2 flow
at different temperatures for 4 h: (b) 280 °C, (c) 500 °C, and (d) 650 °C.
pared by the one-pot method, which is a result of the synthesis
conditions applied. The synthesis of especially exclusively the or-
dered phase is difficult for alumina, and even more so in the pres-
ence of copper species. However, for the catalytic performance, the
presence of a mix of ordered and worm-like mesopores is not ex-
pected to be crucial. Fig. 6 shows the STEM images of the sample
5Cu–Al-800 after reduction at 280 °C for 4 h. The mesoporous
structure is still maintained after the reduction, and the pore size
is around 6 nm. EDX measurements of several selected areas
(Fig. 6c) indicate a homogeneous distribution of copper through
the whole mesoporous matrix. However, metallic copper particles
were not detected after the reduction at these temperatures, which
could be attributed to their small size. When the sample was fur-
ther treated under hydrogen flow at higher temperature, the small
particles grew and became detectable. From the STEM images
(Fig. 7) of the sample 5Cu–Al-800 after reduction at 650 °C for
4 h, small copper particles (light dots) with the size of around
6 nm were detected. They are well distributed over the entire alu-
mina network in the ordered (Fig. 7a and c) or worm-like (Fig. 7b
and d) mesoporous structures. The presence of the metallic copper
particles was also confirmed by the corresponding wide angle XRD
pattern in samples reduced at high temperatures (Fig. 5d).
The results discussed above show that copper particles are
formed as small particles distributed through the whole crystalline
c-Al2O3 network with large surface area and high thermal stability.
Fig. 6. STEM bright-field (a) and dark-field (b and c) images of the sample 5Cu–Al-
800 after reduction at 280 °C for 4 h. EDS measurements from several selected areas
(see image c) indicate the homogeneous distribution of copper through the
mesoporous matrix.
This makes such solids promising bifunctional catalysts for the
one-step DME synthesis. Fig. 8 presents the CO conversion and
the selectivities of DME and CO2 at different operating tempera-
tures. At 295 °C, a CO conversion of 63% was obtained, which is
lower than the equilibrium conversion (78% for the overall reaction
(Eq. (4)) at 295 °C) [32]. With increasing temperature to 310 °C, CO
conversion almost reaches the equilibrium conversion, which is
caused by the enhanced rate of methanol synthesis and increasing
activity of the c-Al2O3 functionality at higher temperature. Also
CO2 was found in the effluent, and its selectivity is around 25%.
As can be seen from Eq. (2), in addition to DME, water will form
by methanol dehydration. The formed water will react with CO,
leading to the formation of CO2. The selectivity of DME is around
73% when the operating temperature is below 300 °C, indicating
the almost all the CO was converted into DME and CO2. Further
increasing the temperature to 325 °C led to the slight decrease of
both CO conversion and DME selectivity. At higher temperature,
more hydrocarbons were detected. Compared to the published
study on a related catalyst system [24], in which a selectivity to
methanol exceeding 30% in the best case was observed, no metha-
nol was detected here at all investigated temperatures. Methanol
selectivity is most probably governed by the balance between
CO-hydrogenation functionality and acid functionality, which need
to be optimized to achieve the desired performance. In the de-
signed mesoporous Cu/c-Al2O3 bifunctional catalyst, all the copper
sites are well surrounded by the acid sites. Methanol is rapidly con-
 H. Jiang et al. / Microporous and Mesoporous Materials 164 (2012) 3–8
Fig. 7. STEM dark-field images of the sample 5Cu–Al-800 reduced at 650 °C for 4 h. (a) and (c): ordered structure, (b) and (d): worm-like mesoporous structure.
Fig. 8. CO conversion and selectivity of DME and CO2 over 5Cu–Al-800 at different
temperatures. FH2 = 12 mL/min, FCO = 6 mL/min, and FN2 = 2 mL/min. The catalyst
was reduced at 250 °C for 4 h in flowing 5% H2 in N2 prior to the catalytic
measurement.
sumed by methanol dehydration once it forms, leading to the ab-
sence of methanol in the final products.
4. Conclusions
In summary, mesoporous Cu–c-Al2O3 with crystalline walls was
successfully synthesized by a one-pot method via the cooperative
self-assembly of Pluronic P123 and the corresponding metal pre-
cursors in ethanolic solution under acidic conditions. Copper was
formed as very small particles from the crystalline Cu–c-Al2O3 net-
work after its reduction under 5% H2 at high temperature. More-
over, it was found that the mesoporous structure with large
7
surface and good thermal stability did not collapse after the reduc-
tion, and the resulting copper nanoparticles are well distributed
through the entire mesoporous c-Al2O3 network, which makes
the material a promising bifunctional catalyst for one-step DME
synthesis. Preliminary studies show that a CO conversion of 72%
and DME selectivity of 69% can be obtained at 50 bar and 310 °C.
The synthetic route described here could provide the blueprint
also for the one-step synthesis of other metal and metal oxide spe-
cies supported on mesoporous c-Al2O3. This is interesting, since c-
Al2O3 is one of the most important commercial catalyst support
materials. Moreover, an additional conclusion can be drawn with
respect to the required catalytic functionality of the catalysts.
While it is obvious, that both CO hydrogenation activity and acidity
for the coupling step are required, the presence of ZnO, which is
normally assumed to be necessary for methanol synthesis activity,
is not mandatory. The catalyst described by us is highly active
without ZnO. This could open additional options for the prepara-
tion of novel catalysts for this reaction.
Acknowledgments
The authors acknowledge the financial support by BMBF
through DMEEXCO2 project (Grant agreement No. 01RC1108)
and of the Max Planck Society and Fraunhofer-Gesellschaft through
the joint project ‘‘Heterogeneous catalysis – the production of base
chemicals and fuels from renewable resources’’.
References
[1] D.M. Brown, B.L. Bhatt, T.H. Hsiung, Catal. Today 8 (1991) 279.
[2] Q. Ge, Y. Huang, F. Qiu, S. Li, Appl. Catal. A 167 (1998) 23.
[3] V. Vishwanathan, K.W. Jun, J.W. Kim, H.S. Roh, Appl. Catal. A 276 (2004) 251.
[4] J. Xia, D. Mao, B. Zhang, Q. Chen, Y. Zhang, Y. Tang, Catal. Commun. 7 (2006)
362.
[5] G.R. Moradi, S. Nosrati, F. Yaripor, Catal. Commun. 8 (2007) 598.
8 H. Jiang et al. / Microporous and Mesoporous Materials 164 (2012) 3–8

[6] K. Faungnawakij, K. Eguchi, Catal. Surv. Asia 15 (2011) 12. [20] Q. Yuan, H.H. Duan, L.L. Li, Z.X. Li, W.T. Duan, L.S. Zhang, W.G. Song, C.H. Yan,
[7] C. Ledesma, J. Llorca, J. Phys.Chem. C 115 (2011) 11624. Adv. Mater. 22 (2010) 1475.
[8] X.M. Liu, G.Q. Lu, Z.F. Yan, J. Beltramini, Ind. Eng. Chem. Res. 42 (2003) 6518. [21] S.M. Morris, P.F. Fulvio, M. Jaroniec, J. Am. Chem. Soc. 130 (2008) 15210.
[9] C. Baltes, S. Vukojeviu, F. Schuth, J. Catal. 258 (2008) 334. [22] W.Q. Cai, J.G. Yu, C. Anand, A. Vinu, M. Jaroniec, Chem. Mater. 23 (2011) 1147.
[10] S. Vukojevic, O. Trapp, J.D. Grunwaldt, C. Kienre, F. Schuth, Angew. Chem. Int. [23] L.B. Sun, W.H. Tian, X.Q. Liu, J. Phys. Chem. C 113 (2009) 19172.
Ed. 44 (2005) 7978. [24] S.C. Baek, S.H. Kang, J.W. Bae, Y.J. Lee, D.H. Lee, K.Y. Lee, Energy Fuels 25 (2011)
[11] J.W. Bae, H.S. Potdar, S.H. Kang, K.W. Jun, Energy Fuels 22 (2008) 223. 2438.
[12] S.H. Kang, J.W. Bae, H.S. Kim, G.M. Dhar, K.W. Jun, Energy Fuels 24 (2010) 804. [25] Z.R. Zhang, T.J. Pinnavaia, J. Am. Chem. Soc. 124 (2002) 12294.
[13] S.R. Blaszkowski, R.A. van Santen, J. Phys. Chem. B 101 (1997) 2292. [26] S.X. Zhou, M. Antonietti, M. Niederberger, Small 3 (2007) 763.
[14] S.H. Kang, J.W. Bae, K.W. Jun, H.S. Potdar, Catal. Commun. 9 (2008) 2035. [27] T. Kawabata, H. Matsuoka, T. Shishido, D.L. Li, Y. Tian, T. Sano, K. Takehira,
[15] Y. Fu, T. Hong, J. Chen, A. Auroux, J. Shen, Thermochim. Acta 434 (2005) 22. Appl. Catal. A 308 (2006) 82.
[16] D.S. Mao, W.M. Yang, J.C. Xia, B. Zhang, Q.Y. Song, Q.L. Chen, J. Catal. 230 (2005) [28] M. Behrens, I. Kasatkin, S. Kuhl, G. Weinberg, Chem. Mater. 22 (2010) 386.
140. [29] Y. Xing, Z.X. Liu, S.L. Suib, Chem. Mater. 19 (2007) 4820.
[17] K.S. Yoo, J.H. Kim, M.J. Park, S.J. Kim, O.S. Joo, K.D. Jung, Appl. Catal. A 330 [30] Y. Xing, Z.X. Liu, S. Gomez, S.L. Suib, J. Phys. Chem. C 112 (2008) 1446.
(2007) 57. [31] P. Ammendola, R. Chirone, L. Lisi, G. Ruoppolo, G. Russo, J. Mol. Catal. A 266
[18] G.H. Yang, N. Tsubaki, J. Shamoto, Y. Yoneyama, Y. Zhang, J. Am. Chem. Soc. 132 (2007) 31.
(2010) 8129. [32] T. Ogawa, N. Inoue, T. Shikada, Y. Ohno, J. Nat. Gas Chem. 12 (2003) 219.
[19] Q. Yuan, A.X. Yin, C. Luo, L.D. Sun, Y.W. Zhang, W.T. Duan, H.C. Liu, C.H. Yan, J.
Am. Chem. Soc. 130 (2008) 3465.