COMMUNICATION
DOI: 10.1002/chem.200901997
Ultra-Deep Hydrodesulfurization of Diesel Fuels on Trimetallic NiMoW
Sulfide Catalysts
Lu Wang, Yongna Zhang, Yuliang Zhang, Zongxuan Jiang,* and Can Li*[a]
Developing ultra-deep hydrodesulfurization (HDS) cata-
lysts with super high activity has been one of the most chal-
lenging and important subjects because of the increasingly
stringent environmental regulations for the sulfur content in
diesel fuels being enforced throughout the world. Further-
more, it is more difficult to process the residual oil resources
remaining in the earth because the residual oil usually has
high sulfur content and more refractory sulfur-containing
compounds.[1] Currently, the most commonly used HDS cat-
alysts are molybdenum or tungsten sulfide catalysts promot-
ed by cobalt or nickel and supported on porous-alumina,
Co(Ni)Mo(W)/Al2O3. These catalysts have been extensively
investigated in the last few decades and the room to further
improve the HDS performance of the conventional catalysts
is very limited.[2] Therefore, the development of novel HDS
catalysts with super high activity remains a promising but
challenging subject.
In recent years, it has been reported in several patents
that a new NiMoW trimetallic HDS catalyst without a sup-
port, called NEBULA, could achieve much higher HDS ac-
tivity than conventional catalysts.[3] In striking contrast with
the recognition from industry, the preparation and catalytic
performance of such catalysts have been rarely reported in
the literature.[4] For the conventional supported NiMo cata-
lyst, the active phase is the so-called Ni-Mo-S phase, which
consists of sulfide Ni atoms decorating the edges of MoS2
slabs.[5] In the supported NiW catalyst, Ni-W-S phases have
also been detected similar to the Ni-Mo-S phases.[6] Howev-
er, the preparation, structure, and the active phase of unsup-
ported NiMoW catalysts have been rarely reported.[4] In this
[a] Dr. L. Wang, Dr. Y. Zhang, Dr. Y. Zhang, Prof. Z. Jiang, Prof. C. Li
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics
Chinese Academy of Sciences
457 Zhongshan Road, Dalian,116023 (China)
Fax: (+ 86) 411-84694447
E-mail: zxjiang@dicp.ac.cn
canli@dicp.ac.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200901997.
Chem. Eur. J. 2009, 15, 12571 12575  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
work we prepared an unsupported trimetallic NiMoW sul-
fide catalyst by a novel method. The new catalyst can ach-
ieve catalytic activity up to 7.5 times that of the commercial
catalysts in the HDS of diesel. Characterization of the
NiMoW catalyst reveals that the unique multilayered struc-
ture of the NiMoW sulfide catalyst is most possibly respon-
sible for the super high HDS activity.
The precursor of the NiMoW sulfide catalyst was pre-
pared by a surfactant-assisted co-precipitation method from
the starting materials (see Experimental Section) including
basic nickel carbonate followed by a sulfidation process to
obtain the final sulfide catalyst. Different solvents, including
alcohols, and a surfactant were used in the preparation to
improve the morphology of the catalyst. The synthesis reac-
tion was conducted in a liquidsolid phase, involving a solu-
ble tungsten source, a soluble molybdenum source, and an
insoluble nickel source, so the structure of the Ni precursor
could be maintained in the final sulfide catalyst. Different
kinds of basic nickel carbonate were also used to prepare
the NiMoW catalysts. Basic nickel carbonate was used as
the nickel source to prepare the NiMoW precursors with hy-
drotalcite-like structures, which were composed of layered
sheets with positive charge and exchangeable anions located
in the galleries between the sheets. Molybdate and tungstate
anions can be exchanged with OH and CO32 bonded to
nickel hydroxyl sheets in the interlayer galleries of the
NiMoW catalysts. The introduction of mixed solvents and
basic nickel carbonate prepared by the co-precipitation
method in this work greatly affect the morphology of the
NiMoW catalyst. The TEM and SEM images (see Figure S1
in the Supporting Information) of the NiMoW-3 sulfide cat-
alyst show a uniformly distributed nanoparticle with a parti-
cle size of about 20 nm and the species with small sheets of
the catalysts, respectively.
4,6-Dimethyldibenzothiophene (4,6-DMDBT) was used as
a model sulfur-containing molecule in decalin (sulfur con-
tent of 500 ppm) to test the HDS performance of the
NiMoW-3 and the commercial CoNiMoW/Al2O3 catalysts.
The sulfur content of the model compound was reduced
from 500 ppm to 1.5 ppm when the HDS reaction was per-
12571
formed under the following conditions: 593 K, 3.5 MPa, a
weight hourly space velocity (WHSV) of 6 h 1, and a H2/oil
ratio of 600 Nm3 m 3. The overall rate constant for 4,6-
DMDBT HDS with the NiMoW-3 catalyst was at least 2.5
times higher than that of the commercial catalyst at differ-
ent reaction temperatures, while the apparent activation
energy of the NiMoW-3 catalyst was significantly reduced
from 176 kJ mol 1 to 140 kJ mol 1 (Table 1). It is clear that
Table 1. Kinetics parameters for HDS of 4,6-DMDBT on NiMoW-3 and
the commercial CoNiMoW/Al2O3 catalyst.
Catalyst Apparent activation KACHTUNGRE(k1+k2) [  10 5 s 1 g cat 1]
energy [kJ mol 1] 493 K 513 K 533 K 553 K
NiMoW-3 140 22 68 285
CoNiMoW/Al2O3[a] 176 26 116
[a] Commercial catalysts.
the NiMoW sulfide catalyst has higher intrinsic HDS activity
than the commercial CoNiMoW/Al2O3 catalyst.
Figure 1 shows the HDS performance of actual diesel for
the NiMoW-1 catalyst is similar to that of the commercial
catalyst, CoNiMoW/Al2O3, whereas the NiMoW-2 and
Figure 1. Catalytic performance of NiMoW catalysts and commercial cat-
alyst for HDS of actual diesel. Reaction conditions: straight-run diesel
(1400 ppm S), 3.5 MPa, 573 K, WHSV 6 h 1 H2/oil ratio of 600 Nm3 m 3.
NiMoW-3 catalysts exhibit super high HDS activities, which
are 3 and 7.5 times higher, respectively, than the commercial
catalyst according to the specific HDS activity listed in
Table 2. The sulfur level of straight-run diesel could be low-
ered from about 1400 ppm to less than 1 ppm using the
NiMoW-3 sulfide catalyst under the optimal conditions of
593 K, 3.5MPa, WHSV of 3 h 1, and a H2/oil ratio of 600
Nm3 m 3.
Considering the different contents of active metals in
NiMoW-3 and the commercial catalysts, we conducted the
element analysis of these two catalysts. The active metal
content in NiMoW-3 is 76.3 wt % with a molar ratio of
Ni:Mo:W of 5.3:1:1.2, whereas it is 23.7 wt % in the com-
12572 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Table 2. The preparation and catalytic activity of the sulfide catalysts.
Catalyst Solvent[a] Basic Surface Specific
nickel area HDS
carbonate[b] ACHTUNGRE[m2g 1] activity[c]
NiMoW-1 H2O commercial 50 123
NiMoW-2 EG + H2O + S commercial 50 306
NiMoW-3 EG + H2O + S laboratory- 56 753
prepared
commercial CoNi- 125 100
MoW/Al2O3
[a] EG denotes ethylene glycol; S denotes surfactant of Triton X-100.
[b] The commercial basic nickel carbonate is purchased from Aldrich,
and the laboratory-prepared compound was synthesized by a co-precipi-
tation method. [c] The HDS activity of the commercial reference catalyst
is defined as 100. The feedstock is straight-run diesel (1400 ppm S).
513
mercial catalyst with a molar ratio of Co:Ni:Mo:W of
1.7:1.1:2.9:1. On the basis of the same weight of active
metal, the HDS activity of NiMoW-3 is about 2.3 times
higher than that of the commercial catalyst.
Figure 2 shows the XRD patterns of the precursor and
the NiMoW sulfide catalysts. The XRD patterns of the
NiMoW sulfide catalysts are in agreement with those of
Figure 2. XRD patterns of NiMoW-3 precursor and NiMoW sulfide cata-
lysts.
poorly crystallized Ni7S6 (JCPDS 14-0364), MoS2 (JCPDS
17-0744), and WS2 (JCPDS 35-0651). The XRD diffraction
peaks of bulk Ni7S6 are much more intense for NiMoW-2
and NiMoW-3, mainly owing to the presence of organic sol-
vent and surfactant. The use of laboratory-prepared basic
nickel carbonate has a remarkable influence on the structure
and HDS activity of the NiMoW sulfide catalyst because the
structures of the laboratory-prepared and commercial nickel
sources are different according to the XRD patterns of the
Ni precursors (see Figure S2 in the Supporting Information).
The XRD peaks of the laboratory-prepared basic nickel car-
bonate are in good agreement with the hydrotalcite-like
structure reported before.[3] It is easy for Mo and W species
to exchange with the anions in the galleries of the nickel
source sheets. Furthermore, the characterization peaks of
the hydrotalcite-like structure at 408 and 588 also appeared
Chem. Eur. J. 2009, 15, 12571 12575
Hydrodesulfurization of Diesel Fuels
COMMUNICATION
in the sulfide catalyst. It is suggested that the hydrotalcite-
like basic nickel carbonate with layered sheets is retained in
both the precursor and the final sulfide catalysts.
The multilayered structure is also revealed by EXAFS
(see Figure S3 in the Supporting Information). EXAFS spec-
tra of the Mo K-edge, the W L3-edge, and the Ni K-edge
were measured for the oxide precursors of NiMo, NiW, and
NiMoW catalysts. In the Ni K-edge EXAFS spectra (see
Figure S3(c) in the Supporting Information), the peaks ap-
peared periodically with the coordination distances at about
2.62 , 4.75 , and 6.92 , which are assigned to NiNi con-
tributions in the NiMoW-3 species.[7] Combining the results
of XRD and EXAFS, it is confirmed that the hydrotalcite-
like nickel species with multilayer structure are formed in
the oxide precursors and may be retained in the final sulfide
catalysts described in this work.
To investigate the structure of the NiMoW catalysts, XPS,
SEM, EDX, and HRTEM analyses were conducted. In the
XPS spectra of NiMoW sulfide catalysts (see Figure S4 in
the Supporting Information), the peak intensity in Ni 2p
spectra (see Figure S4(c)) is much weaker than that in the
Mo 3d and W 4f spectra for all three catalysts.[8] The
amount of Ni species exposed to the surface is too low to be
detected by XPS in NiMoW-3. So we propose a structure in
which the Ni species are probably covered by Mo, W, or
MoW sulfides on the surface of the sulfide catalysts. The
SEM images of NiMoW-3 (Figure 3a) show a similar struc-
ture. From a combined SEM and EDX characterization, we
confirmed that the Mo and W sulfide particles are support-
ed by bulk Ni7S6 particles and are dispersed well on the sur-
face and the interlayer galleries of the support in the
NiMoW catalysts. A multilayered structure model of the
NiMoW catalyst is presented in Figure 3a. A multilayered
structure for the catalyst is also observed in the HRTEM
images (see Figure 3b). Here the Ni7S6 species with a basal
spacing of 2.86  are covered by curved slabs of WS2 and Figure 3. a) SEM image and elemental analysis by EDX of the NiMoW-3
MoS2 with a basal spacing of 6.15 . sulfide catalyst and b) HRTEM image of the NiMoW-3 sulfide catalyst.
The catalyst has been reported to exhibit higher intrinsic
HDS activity when the values of R (atomic ratio of Ni/
ACHTUNGRE(Ni+W)) are in the range of 0.80.9 and the Ni sulfide parti-
cles are surrounded by a few layers of WS2.[9] For NiMo cat- the HRTEM images (see Figure 3b). The average slab
alysts, the increased HDS activity at high atomic ratios of Ni length and the degree of stacking of the MoS2 or WS2 are
to Mo has been attributed to the active MoS2 phase support- estimated to be 27 nm and 38 slabs, respectively. Com-
ed by NiS particles.[10] In this work, when the ratio of Ni to pared with the data on the supported NiMo catalyst from a
(Ni + Mo + W) was 0.65, similar phenomena could also be previous report,[11] the NiMoW catalyst in this work has
observed. And this effect may be responsible for the super more stacking layers and a comparative slab length. The
high HDS activity of the NiMoW catalyst. slabs are dispersed well on nickel sulfide lattice fringes. Fur-
In the sulfide NiMoW catalyst, some hydrotalcite-like Ni thermore, some composite sulfide structures are formed in
species remain, while other parts are changed to Ni7S6 after the galleries between the Ni sulfide layers (see Figure 3b).
sulfidation and retain the multilayered structure. It is pro- We also characterized the NiMoW catalysts by Raman
posed that a multilayered structure, in which Mo and W spe- spectroscopy (see Figure S5 in the Supporting Information).
cies are dispersed on the surface and the interlayer galleries In the Raman spectra of the NiMoW sulfide catalyst the
of the bulk Ni7S6 support, has a greater tendency for the new peak at 411 cm 1 for NiMoW-3 was assigned to Mo-W
decoration of the WS2, MoS2, and MoxW1 xS2 slabs edges by composite species. The Mo-W composite species could then
Ni atoms, and finally for the formation of more Ni-Mo-S, be interacted with Ni species to form Ni-Mo-W-S active spe-
Ni-W-S, and Ni-Mo-W-S active sites. Crystalline lattice fring- cies. These phases exhibit excellent HDS activity.[12] The
es of WS2, MoS2, and Ni-S can be clearly distinguished in HDS active sites were mainly at the curvature of the basal

Chem. Eur. J. 2009, 15, 12571 12575  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 12573
 C. Li, Z. Jiang et al.

planes and the edge planes of the active metal sulfide.[13] In promise for application in HDS to produce clean diesel with
this work, considering the multilayered structure of hydro- ultra low sulfur content.
talcite-like Ni species, these active species appear to be
mainly located at the interfaces between the deposited spe-
cies of WS2, MoS2, or MoxW1 xS2 and the Ni sulfide support Experimental Section
species.
Scheme 1 describes the formation of the NiMoW catalyst Preparation of NiMoW sulfide catalysts: The sulfide catalysts were syn-
thesized in two steps. First, the precursor was prepared by means of a sur-
in which Mo, W, or MoW sulfides are deposited on the sur-
factant-assisted co-precipitation method from ammonium molybdate
face and interlayer galleries of the bulk Ni7S6 support. Then (0.040 mol), ammonium metatungstate
(0.023 mol), and basic nickel carbonate
(0.033 mol) in different solvents in-
cluding ethylene glycol, water, and
Triton X-100. Then the precursor was
sulfided at 673 K for 2 h by using
10 vol % H2S/H2, before the characteri-
zation or HDS reaction. The laborato-
ry-prepared basic nickel carbonate was
synthesized by using a co-precipitation
method with the reactants of Ni-
ACHTUNGRE(OAc)2 and Na2CO3 in mixed solvents.
Characterization: XRD patterns were
obtained on a Rotaflex (Ru-200b)
powder X-ray diffractometer with
CuKa radiation and were collected
from 10 to 808 at a speed of 58 min 1.
Elemental analyses were conducted on
a Magix-2424 X-ray fluorescence anal-
ysis diffractometer. SEM images were
examined with a QUANTA 200F in-
strument. HRTEM images were ob-
tained on a Tecnai G2 F30 S-Twin
(FEI Company) instrument. X-ray
photoelectron spectra (XPS) of the
catalyst samples were recorded on a
KROTOS AMICAS spectrometer
Scheme 1. Formation of the NiMoW sulfide catalyst with multilayered structure. (Shimadzu, Japan) with a magnesium
Ka (hn = 1253.6 eV) radiation source.
Charging effects were corrected by ad-
justing the binding energy of C 1s to
the composite active phases such as Ni-Mo-S, Ni-W-S, and 284.8 eV. Visible Raman spectra were recorded on a JobinYvon U1000
scanning double monochromator with a spectral resolution of 4 cm 1.
the new species Ni-Mo-W-S are formed at the interface be-
The line at 532 nm from a DPSS 532 Model 200 532 nm single-frequency
tween the bulk Ni-S support and the deposited species. Fur- laser was used as the excitation source. The spectra of EXAFS were mea-
thermore, because of the unique layered structure of basic sured at the beam line of 4WIB of Beijing Synchrotron Radiation Facility
nickel carbonate, it is assumed that the interface area be- (BSRF) using a double-crystal Si (111) monochromator. EXAFS spectra
tween the Ni-S support and the deposited Mo and W sulfide of Mo K-edge (20 000 eV), Ni K-edge (8333 eV), and W L3-edge
(10 207 eV) were measured in transmission mode. The sample thickness
species is much greater in the catalyst NiMoW-3, and thus
was chosen to give an absorption edge step of about 1.0 near the edge
more active sites, such as Ni-Mo-S, Ni-W-S, and Ni-Mo-W-S, region.
are formed in this catalyst. The kinetics parameters for the HDS of 4,6-DMDBT (500 ppm S in deca-
In summary, we have reported a novel trimetallic NiMoW lin) were determined while the conversions of 4,6-DMDBT were lower
catalyst with super high HDS activity. The NiMoW sulfide than 20 %. The total sulfur content was determined by microcoulometry
(detection limit, 0.1 ng mL 1). The overall rate constant and apparent acti-
catalyst exhibits a much higher HDS performance than that
vation energy listed in Table 1 were obtained from the experimental data
of the commercial catalyst in the HDS of actual diesel. In based on pseudo-first-order kinetics.[14]
the HDS of 4,6-DMDBT, the NiMoW catalyst exhibits
higher intrinsic HDS activity than commercial catalysts, in
which the apparent activation energy is lower from
176 kJ mol 1 to 140 kJ mol 1. This super high HDS activity is
achieved mainly by forming a unique multilayered structure
of the NiMoW sulfide catalyst, in which the Ni7S6 species Acknowledgements
with layered structure act as a support for Mo, W, or MoW
This work was supported by the National Natural Science Foundation of
sulfide particles. The Ni-Mo-W-S species with much higher China (NSFC Grant No. 20673114) and the State Key Project of China
activity are derived in the catalyst with multilayered struc- (No. 2006CB202506). We would like to acknowledge the Beijing Syn-
ture. The NiMoW catalyst reported in this work shows chrotron Radiation Facility (BSRF) for the EXAFS data.

12574 www.chemeurj.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2009, 15, 12571 12575
Hydrodesulfurization of Diesel Fuels
Keywords: 4,6-dimethyldibenzothiophene diesel NiMoW
sulfide catalyst ultra-deep hydrodesulfurization
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Received: July 20, 2009
Published online: October 27, 2009
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