Applied Catalysis A: General 351 (2008) 189194

Contents lists available at ScienceDirect

Applied Catalysis A: General

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

High resistance to carbon deposition of silica-coated Ni catalysts in propane

stream reforming
Sakae Takenaka *, Yoshiki Orita, Hiroshi Umebayashi, Hideki Matsune, Masahiro Kishida *
Department of Chemical Engineering, Graduate School of Engineering, Kyushu University, Moto-oka 744, Nishi-ku, Fukuoka 819-0395, Japan

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 27 June 2008
Received in revised form 16 September 2008
Accepted 17 September 2008
Available online 1 October 2008

The catalytic performance of Ni metal catalysts uniformly covered with layers of silica for propane steam
reforming was compared with the performances of Ni metal catalysts supported on substrates of
magnesia (MgO), alumina (Al2O3) and silica (SiO2). The silica-coated Ni catalysts showed high activity for
propane steam reforming at 873 K. This catalytic activity is higher than the activity of effective light
alkane steam reforming Ni/Al2O3 and Ni/MgO catalysts and we found that the catalytic activity of the
silica-supported Ni metal was poor. The coverage of Ni metal particles with silica thus improves their
catalytic activity for this reaction. Carbon deposition on silica-coated Ni catalysts during the steam
reforming of propane at 873 K was lower than that on Ni/MgO and Ni/Al2O3. Ni K-edge XANES and EXAFS
spectra of silica-coated Ni catalyst showed a strong interaction between Ni metal and silica. This
interaction prevents the sintering of Ni metal particles during the propane steam reforming, which
results in the reduction of carbon deposition on silica-coated Ni catalysts. These properties of silicacoated Ni catalysts result in high catalytic activity and improved catalyst stability.
2008 Elsevier B.V. All rights reserved.

Keywords:
Propane steam reforming
Synthesis gas
Ni catalysts
Silica coating
Carbon deposition

1. Introduction
H2 is a clean fuel because CO2 is not emitted when it is used as a
fuel for polymer-electrolyte fuel cells (PEFCs). H2 has been
produced through steam reforming of CH4, which is a main
component of natural gas, followed by a water-gas shift reaction of
CO. Supported Ni catalysts are generally used for the steam
reforming of CH4 [15]. These catalysts are, however, deactivated
by the sintering of Ni metal and by coke formation. The
development of Ni catalysts which are resistant to Ni metal
particle sintering and to coke formation is thus desired.
Steam reforming of CH4 is a promising technology for the
supply of H2 to stationary fuel cells due to an abundance of CH4 as
natural gas and as CH4 hydrate. H2 production facilities should be
constructed near natural gas pipelines due to energy costs
associated with storage and transportation of liqueed natural
gas. The energy requirement is due to the low liquefaction
temperature of CH4. Urban infrastructure exists for the distribution
of CH4 as utility gas but remote locations need alternative energy
sources for H2 production. Liqueed petroleum gas (LPG), which
mainly contains propane, is a promising alternative energy source
for H2 production because LPG is condensed at higher tempera-

tures than natural gas. The steam reforming of LPG should thus be
investigated for the potential use in fuel cells. Supported Ni
catalysts have been investigated for the use in the steam reforming
of LPG but were found to be deactivated by coke formation [610].
These reports indicated that the formation of coke is more
pronounced in the steam reforming of LPG than in the steam
reforming of natural gas. The development of Ni catalysts with high
resistance to coke formation is thus desired.
Our group has previously reported excellent catalytic performance for the partial oxidation of CH4 into synthesis gas using a
silica-coated Ni catalyst [11]. The Ni metal nanoparticles within
the silica-coated Ni catalyst were not aggregated during the partial
oxidation of CH4 at 973 K because they were uniformly covered by
layers of silica. In addition, this catalyst was not deactivated by
coke formation during the partial oxidation of CH4. This study was
undertaken with the expectation that silica-coated Ni catalysts
would be effective for the steam reforming of LPG. The silicacoated Ni metal catalyst was thus applied to the steam reforming
of propane.
2. Experimental
2.1. Preparation of catalysts

* Corresponding authors. Tel.: +81 92 802 2752; fax: +81 92 802 2752.
E-mail address: takenaka@chem-eng.kyushu-u.ac.jp (S. Takenaka).
0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.09.017

The Ni catalyst coated with silica (denoted as coat-Ni hereafter)

was prepared by using a water-in-oil microemulsion [1214]. The

S. Takenaka et al. / Applied Catalysis A: General 351 (2008) 189194

190

microemulsion was prepared by adding aqueous nickel nitrate

(Ni(NO3)2) into a solution of surfactant (polyoxyethylene (n = 15)
cetyl ether and cyclohexane). Nanoparticles of a compound
containing Ni cations were synthesized by the addition of
hydrazine (N2H4H2O) to the microemulsion. Hydrolysis and
polycondensation of tetraethyl orthosilicate (TEOS) was done at
333 K by the addition of TEOS and aqueous ammonia (NH3) to the
microemulsion. The precipitates obtained were washed with
isopropanol several times and calcined at 773 K for 2 h under an air
stream. To avoid an explosion involving the Ni metal precursor
during calcination of the catalysts in air, only a small amount of the
catalyst was calcined. The calcined samples were washed with
nitric acid (HNO3, 1.0 M) at room temperature in order to remove
any Ni species which were not covered by silica. After this
treatment, the Ni loading was estimated with X-ray uorescence
spectroscopy (XRF). Silica-supported Ni catalysts (Ni/SiO2), magnesia-supported Ni catalysts (Ni/MgO) and alumina-supported Ni
catalysts (Ni/Al2O3) were prepared with a conventional impregnation method. Briey, MgO (JRC-MGO4-500A from the Catalysis
Society of Japan), Al2O3 (JRC-ALO-8 from the Catalysis Society of
Japan) or SiO2, which was prepared by the hydrolysis and
polycondensation of TEOS, was added to aqueous Ni(NO3)2 at
353 K and then dried at 353 K. The dried samples were calcined at
873 K for 5 h under an air stream. These catalyst samples were
pressed into a disc and crushed to 1628 mesh prior to reaction
testing.
2.2. Reaction procedure
Steam reforming of propane was done at atmospheric pressure
with a conventional gas ow system containing a xed catalyst
bed. The catalyst samples, diluted with quartz sand, were packed
into a tubular quartz reactor (length = 300 mm and inner
diameter = 8 mm). The catalysts were reduced with H2 at 973 K
for 1 h before the reactions. After catalyst pretreatment, a mixed
gas of propane and steam, diluted with Ar was introduced into the
reactor at 873 K. Efuent gases from the catalyst bed were sampled
and analyzed by on-line gas chromatography. The yield of H2 and
selectivity to CO, CO2 or CH4 are dened as follows:
Yield of H2 %

973 K. After the treatment, the catalysts were packed into a

polyethylene bag under an Ar atmosphere. Analysis of the EXAFS
data was done using REX (Rigaku Co.), an EXAFS analysis program.
A Fourier transformation of the k3-weighted EXAFS oscillation was
done over the range of k = 3.515.5 A1.
The quantity of carbon deposited on the Ni catalysts during the
steam reforming of propane was evaluated by thermogravimetric
analysis under an air stream. During the experiments, the catalyst
samples were heated to 1023 K under air, which resulted in the
gasication of deposited carbon.
3. Results and discussion
3.1. Structure of the Ni species in the catalysts
Fig. 1 shows a TEM image of coat-Ni after reduction with H2
at 973 K as well as the TEM image of Ni/SiO2 for comparison. In
the TEM image of Ni/SiO2, small particles of 520 nm in
diameter are attached to the outer surface of the silica supports.
As described below, the small particles observed in the TEM
image for Ni/SiO2 are assigned to Ni metal. The TEM image of
coat-Ni shows small particles with diameters of ca. 5 nm within
spherical silica particles of ca. 50 nm diameter. The small
particles in coat-Ni are also assigned to Ni metal as described
below. In the TEM image of coat-Ni, Ni metal particles are
always located at the center of the spherical silica particles. The
Ni metal particle in coat-Ni is thus stabilized within the
spherical silica particle, whereas Ni metal particles in Ni/SiO2,
are attached to the outer surface of silica.
Fig. 2 shows XRD patterns of coat-Ni, Ni/MgO, Ni/Al2O3 and Ni/
SiO2. The catalyst samples were reduced with H2 at 973 K before
measuring XRD patterns but were brought into the contact with
air, at room temperature, during the XRD measurement. Diffraction lines due to Ni metal crystallites are observed at about 44.58

2  moles of H2 produced
 100
total moles of H atoms in the feed

Selectivity to CO; CO2 or CH4 %



moles of CO; CO2 or CH4
 100

3  moles of propane converted

2.3. Characterization of the catalyst samples
TEM images of the Ni catalysts were recorded with a JEOL JEM2000EX. Before TEM image collection, the catalyst samples were
reduced with H2 at 973 K. The reduced samples were dispersed in
2-propanol at room temperature and then an aliquot of the
solution was dropped on a grid for the measurement of TEM
images.
Measurement of X-ray absorption spectra (X-ray absorption
near edge structure, XANES and extended X-ray absorption ne
structure, EXAFS) was done on the beam line, BL 7C, at the Photon
Factory in the Institute of Materials Structure Science for High
Energy Accelerator Research Organization, Tsukuba, Japan (Proposal No. 2005G194). Ni K-edge XANES/EXAFS spectra of the Ni
catalysts were measured in transmission mode with a Si(1 1 1)
two-crystal monochromator at room temperature with a ring
energy of 2.5 GeV and a stored current of 250450 mA. Before the
spectra were obtained, the catalysts were reduced with H2 at

Fig. 1. TEM images of Ni(10 wt%)/SiO2 (a) and coat-Ni(10 wt%) (b).

S. Takenaka et al. / Applied Catalysis A: General 351 (2008) 189194

Fig. 2. XRD patterns of Ni(10 wt%)/MgO, Ni(10 wt%)/SiO2, Ni(20 wt%)/Al2O3 and
coat-Ni (10 wt%).

and 52.08 in the XRD patterns for all the Ni catalysts. These peaks,
however, have a low intensity for coat-Ni and Ni/MgO but the
results do indicate that Ni metal crystallites are present in all the Ni
catalysts. The formation of a solid solution between NiO and MgO
is known to occur and the Ni species within the solid solution are
not easily reduced to Ni metal in the presence of H2, even at 973 K
[15]. The diffraction lines due to Ni metal in the XRD pattern of Ni/
MgO are, therefore, very small in intensity.

Fig. 3. Ni K-edge XANES spectra of different Ni catalysts and reference samples (Ni
foil and NiO). (a) Ni foil; (b) Ni (10 wt%)/SiO2; (c) Ni (20 wt%)/Al2O3, (d) coat-Ni
(10 wt%); (e) Ni (10 wt%)/MgO; (f) NiO.

191

Fig. 3 shows the Ni K-edge XANES spectra of coat-Ni, Ni/MgO,

Ni/Al2O3 and Ni/SiO2. XANES spectra for the reference samples
(NiO and Ni foil) are also shown in Fig. 3. The XANES spectrum of
NiO is markedly different from that of Ni foil, i.e. a strong
absorption at about 8350 eV is observed in the XANES spectrum of
NiO, whereas the peak intensity at around 8350 eV for Ni foil is
very small. The XANES spectrum reveals useful information about
the oxidation state of the Ni species in the catalysts [16]. The
XANES spectra of Ni/SiO2 and Ni/Al2O3 are similar to the spectrum
of Ni foil; therefore, most of the Ni species in Ni/SiO2 and Ni/Al2O3
are present as Ni metal. The XANES spectrum of Ni/MgO is more
similar in shape to the spectrum of NiO rather than the spectrum of
Ni foil. A small shoulder peak at about 8333 eV, which is
characteristic of XANES spectrum for Ni foil, is found in the
XANES spectrum of Ni/MgO. This peak suggests that some Ni
species in Ni/MgO is present as Ni metal, although Ni species would
exist, mainly, in the oxidized state. The XANES spectrum of coat-Ni
resembles the spectrum of Ni foil more closely than the spectrum
of NiO. The peak at about 8350 eV in the XANES spectrum of coatNi is slightly more intense than that for Ni foil. This indicates that
some Ni species in coat-Ni are in the oxidized state, while most Ni
species are present as Ni metal. The XANES spectrum of Ni/SiO2
shows that the fraction of oxidized Ni species to total Ni species in
coat-Ni is higher than that in Ni/SiO2. The higher oxidation ratio
implies that the Ni species in coat-Ni have a strong interaction with
the silica layers.
Fig. 4 shows Fourier transforms of Ni K-edge k3-weighted EXAFS
spectra (RSFs, radial structural functions) for coat-Ni, Ni/MgO, Ni/
Al2O3, Ni/SiO2 and Ni foil. A peak is observed at about 2.1 A in the
RSFs for all the Ni catalysts as well as for Ni foil. This peak is
assigned to the rst NiNi shell of Ni metal. The intensity of the
peak in the RSFs strongly depends on the type of Ni catalyst, i.e. the
peak intensity decreases in the following order: Ni/SiO2 > Ni/
Al2O3 > coat-Ni > Ni/MgO. The peak intensity due to the rst shell
in the RSF for any metal is dependent on the crystallite size of the
metal [17,18]. The average crystallite size of Ni metal in the Ni
catalysts used in this study thus increases in the following order:
Ni/SiO2 > Ni/Al2O3 > coat-Ni > Ni/MgO. Intense peaks are not
found in the range R > 2.5 A in the RSF for Ni/MgO, although the

Fig. 4. Fourier transforms of Ni K-edge k3-weighted EXAFS spectra for different Ni

catalysts and Ni foil. (a) Ni(10 wt%)/MgO; (b) coat-Ni(10 wt%); (c) Ni(20 wt%)/
Al2O3; (d) Ni(10 wt%)/SiO2; (e) Ni foil.

S. Takenaka et al. / Applied Catalysis A: General 351 (2008) 189194

192

RSF for NiO has an intense peak at around 2.7 A due to the second
shell (NiNi) in NiO (the result is not shown). Oxidized Ni species in
Ni/MgO are, therefore, not aggregated but highly dispersed in the
MgO supports, i.e. the formation of a Ni-Mg-O solid solution
occurs.
3.2. Catalytic performance of coat-Ni for steam reforming of propane
Ni/MgO and Ni/Al2O3 catalysts are some of the most effective
catalysts for the steam reforming of light alkanes such as CH4,
ethane and propane. The catalytic performance of coat-Ni for the
steam reforming of propane was thus compared with the
performances of Ni/MgO and Ni/Al2O3. Propane conversion and
H2 yield in the steam reforming of propane over Ni/MgO, Ni/Al2O3
and coat-Ni catalysts with different Ni loading are listed in Table 1.
The quantity of catalyst loaded into the reactor was such that the
Ni content was equivalent in all the reactions. The results shown in
Table 1 were collected at 5 h of time on stream, from the reaction
over each catalyst. H2, CO, CO2 and CH4 were formed in addition to
trace amounts of ethylene and propylene during all the Ni catalyst
reactions. The H2 yield and propane conversion over coat-Ni and
Ni/Al2O3 increased with higher Ni loading. In contrast to coat-Ni
and Ni/Al2O3, the catalytic activity of Ni/MgO for the steam
reforming of propane was lower when the Ni loading increased
from 10 to 20 wt%. The catalytic reactions of Ni (10 wt%)/MgO,
coat-Ni (10 wt%) and Ni (20 wt%)/Al2O3 were then examined.
Table 1 also shows the results of propane steam reforming over the
Ni (10 wt%)/SiO2 catalyst, which was prepared by a conventional
impregnation method. The Ni/SiO2 catalyst did not show any
activity for the steam reforming of propane as no H2 or CO was
formed under the experimental conditions. It was reported that Ni/
SiO2 catalysts were easily deactivated for the steam reforming of
methane [19,20]. The results shown in Table 1 were collected at 5 h
of time on stream. Thus, the Ni/SiO2 would be deactivated at 5 h of
time on steam. Likely, the silica coating of coat-Ni improves the
catalytic activity of the Ni metal for the steam reforming of
propane.
Steam reforming of propane over coat-Ni, Ni/MgO and Ni/Al2O3
catalysts was carried out with different W/F values (W, weight of Ni
atoms in the reactor; F, ow rate of reactants) in order to assess the
catalytic activity of each catalyst. Fig. 5 shows propane conversion
after 5 h of time on stream, as a function of W/F values from the
reactions over the coat-Ni, Ni/MgO and Ni/Al2O3 catalysts. W/F
values ranged from ca. 0.01 to 0.04. All the Ni catalyst reactions had
lower propane conversion as the W/F ratio was reduced. The
propane conversion for coat-Ni was higher than for the other
catalysts over the whole W/F range, indicating that the coat-Ni
catalysts, generally, had the highest activity. As described
previously, the Ni metal crystallites in coat-Ni are smaller than
those in Ni/Al2O3, which also contributes to the higher catalytic
activity of coat-Ni. On the other hand, the Ni metal crystallites in
Ni/MgO are also small, but the fraction of Ni metal to all Ni species

Fig. 5. Change of propane conversion as a function of W/F in the propane steam

reforming over coat-Ni, Ni/MgO and Ni/Al2O3 catalysts at 873 K. P(C3H8) = 5 kPa,
P(H2O) = 15 kPa, P(N2) = 5 kPa and P(Ar) = 76 kPa.

in Ni/MgO is signicantly lower than that in coat-Ni. This is

conrmed by the XANES and EXAFS spectra. The catalytic activity
of Ni/MgO for the steam reforming of propane was thus lower than
the catalytic activity of coat-Ni.
Fig. 6 shows the change of propane conversion with time on
stream in the propane steam reforming over coat-Ni, Ni/MgO and
Ni/Al2O3. In these reactions, the molar ratio of propane to steam
was adjusted to 1/3. The change of H2 yield and selectivity to CO,
CO2 and CH4 as a function of time on stream in these reactions is
plotted in Fig. 7. The conversion of propane for coat-Ni was always
higher than the propane conversions for Ni/MgO and Ni/Al2O3
catalysts. The coat-Ni catalysts showed slight deactivation initially
and then stabilized after 3 h on stream. The catalytic activities of
Ni/MgO and Ni/Al2O3 were also depressed slightly with time on
stream. The deactivation of these catalysts is due to carbon
deposition during the reactions. In contrast to propane conversion,
the H2 yield for coat-Ni did not decrease appreciably during
propane steam reforming. The H2 yield and CH4 selectivity for coatNi were higher than the H2 yield and CH4 selectivity of the other
catalysts. On the other hand, the CO2 selectivity of coat-Ni was

Table 1
Steam reforming of propane over coat-Ni, Ni/MgO, Ni/Al2O3 and Ni/SiO2 at 873 K.
Catalyst

Ni loading (wt%)

Conversion of C3H8 (%)

H2 yield (%)

Coat-Ni
Coat-Ni
Ni/MgO
Ni/MgO
Ni/Al2O3
Ni/Al2O3
Ni/SiO2

5
10
10
20
10
20
10

21
98
89
46
62
86
<1

21
65
68
42
61
67
0
1

Composition of reactants, C3H8:H2O:N2:Ar = 1:3:1:15; ow rate = 100 ml min

loading mass of Ni in the reactor = 0.0025 g.

Fig. 6. Change of propane conversion with time on stream in the propane steam
reforming over coat-Ni, Ni/MgO and Ni/Al2O3 at 873 K. P(C3H8) = 5 kPa,
P(H2O) = 15 kPa, P(N2) = 5 kPa and P(Ar) = 76 kPa. Flow rate = 100 ml min1. Mass
of Ni in the reactor = 0.0013 g.

S. Takenaka et al. / Applied Catalysis A: General 351 (2008) 189194

193

Fig. 8. Change of propane conversion with time on stream in the propane steam
reforming over coat-Ni, Ni/MgO and Ni/Al2O3 at 873 K. P(C3H8) = 5 kPa,
P(H2O) = 20 kPa, P(N2) = 5 kPa and P(Ar) = 71 kPa. Flow rate = 100 ml min1. Mass
of Ni in the reactor = 0.0013 g.

Fig. 7. Change of H2 yield and selectivity to CO, CO2 or CH4 with time on stream in
the propane steam reforming over coat-Ni, Ni/MgO and Ni/Al2O3 at 873 K.
P(C3H8) = 5 kPa, P(H2O) = 15 kPa, P(N2) = 5 kPa and P(Ar) = 76 kPa. Flow rate = 100
ml min1. Mass of Ni in the reactor = 0.0013 g.

lower than those for the Ni/MgO and Ni/Al2O3 catalysts. The
selectivity to CO was similar for all the catalysts. These results
imply that methanation of CO2 preferentially occurs over the coatNi catalyst.
In a further experiment, the molar ratio of propane to steam in
the steam reforming of propane was changed from 1/3 to 1/4. The
change in propane conversion and the change in H2 yield as well as
the selectivity to CO, CO2 and CH4 as a function of time on stream
are shown in Figs. 8 and 9, respectively. Propane conversions for
the reactions over coat-Ni and Ni/Al2O3 catalysts were higher
when the partial pressure of steam was increased, while the
propane conversion for Ni/MgO did not depend appreciably on the
partial pressure of steam. All the catalysts deactivated slightly with
time on stream, but the rate of deactivation was negligible
compared to the reactions at the propane/steam ratio = 1/3. The
increase in the partial pressure of steam is likely to mitigate the
carbon deposition on the Ni catalysts during the steam reforming
of propane. The selectivity to CO, CO2 and CH4 for all the catalysts
did not depend, signicantly, on the partial pressure of steam.
The amount of carbon deposited on the Ni catalysts during the
reactions for 5 h is shown in Fig. 10. The amount of carbon
deposited on the coat-Ni was signicantly less than the amounts of
carbon deposited on Ni/MgO and Ni/Al2O3. The coat-Ni catalyst
showed high resistance to carbon deposition in the reaction even at
lower partial pressures of steam. The amount of carbon deposited
on the supported Ni catalysts during the steam reforming of

Fig. 9. Change of H2 yield and selectivity to CO, CO2 or CH4 with time on stream in
the propane steam reforming over coat-Ni, Ni/MgO and Ni/Al2O3 at 873 K.
P(C3H8) = 5 kPa, P(H2O) = 20 kPa, P(N2) = 5 kPa and P(Ar) = 71 kPa. Flow rate = 100
ml min1. Mass of Ni in the reactor = 0.0013 g.

194

S. Takenaka et al. / Applied Catalysis A: General 351 (2008) 189194

carbon deposition of coat-Ni catalysts during the steam reforming

of propane. These factors result in high catalytic activity and
improved stability of coat-Ni for the reaction.
4. Conclusion
Silica-coated Ni catalysts show high catalytic activity and
improved stability in the steam reforming of propane. The silicacoated Ni catalysts had reduced carbon deposition during propane
steam reforming, compared to Ni/Al2O3 and Ni/MgO, which are
some of the most effective catalysts for the steam reforming of
hydrocarbons. The strong interaction of Ni metal particles with
silica, in the silica-coated Ni catalysts, prevents the sintering of Ni
metal and carbon deposition during the steam reforming of
propane. These properties of the silica-coated Ni catalyst resulted
in excellent catalytic performance.
Fig. 10. The amount of carbon deposited on coat-Ni, Ni/MgO and Ni/Al2O3 during
the steam reforming of propane at 873 K.

hydrocarbons generally increases as the conversion of hydrocarbons increases. The catalytic activity of coat-Ni was higher than
that of the other catalysts tested in this study. We thus conclude
that the coat-Ni catalyst has a high resistance to carbon deposition
during the steam reforming of hydrocarbons. Carbon deposition
from hydrocarbons on the supported Ni catalysts is more prevalent
when the Ni metal particle is larger [2123]. As previously
described, Ni metal particles in coat-Ni were smaller than those in
Ni/Al2O3. The Ni metal particles in coat-Ni are not aggregated
during the propane steam reforming because the metal particles
are covered with silica. Thus, coat-Ni catalyst has a high resistance
to carbon deposition during the steam reforming of propane. It is
reported that carbon is deposited as lamentous carbon during the
steam reforming of hydrocarbons over the supported Ni catalysts
[24,25]. Carbon atoms from hydrocarbons are deposited on the
surface of Ni metal particles, supported on carriers, during the
steam reforming of hydrocarbons, and then carbon atoms diffuse
on the surfaces and/or in the bodies of the Ni metal particles,
resulting in the formation of lamentous carbon [26,27]. Ni metal
particles in the supported Ni catalysts are thus not present on the
carrier, but are present at the tip of lamentous carbon, when
carbons are deposited on the Ni catalysts. It should be noted that Ni
metal particles in coat-Ni are covered with silica layers. The Ni
metal particles in coat-Ni strongly interact with silica, as shown by
its XANES spectrum. The strong interaction between silica and Ni
metal particles in coat-Ni should prevent detachment of Ni metal
particles from silica supports, which results in high resistance to

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]

V.R. Choudhary, B.S. Uphade, A.S. Mamman, Catal. Lett. 32 (1995) 387390.
O. Yamazaki, K. Tomishige, K. Fujimoto, Appl. Catal. A 136 (1996) 4956.
M.A. Pena, J.P. Gomez, J.L.G. Fierro, Appl. Catal. A 144 (1996) 757.
J.N. Armor, Appl. Catal. A 176 (1999) 159176.
T. Shishido, P. Wang, T. Kosaka, K. Takehira, Chem. Lett. (2002) 752753.
nsan, Appl. Catal. A 258 (2004) 235240.
A.K. Avc, D.L. Trimm, A.E. Aksoylu, Z.I. O
S. Natesakhawat, R.B. Watson, X. Wang, U.S. Ozkan, J. Catal. 234 (2005) 496508.
C. Resini, M.C.H. Delgado, L. Arrighi, L.J. Alemany, R. Marazza, G. Buska, Catal.
Commun. 6 (2005) 441445.
O. Sidjabat, D.L. Trimm, Top. Catal. 1112 (2000) 279282.
M. Shiraga, D. Li, I. Atake, T. Shishido, Y. Oumi, T. Sano, K. Takehira, Appl. Catal. A
318 (2007) 143154.
S. Takenaka, H. Umebayashi, E. Tanabe, H. Matsune, M. Kishida, J. Catal. 245 (2007)
390398.
M. Kishida, T. Tago, T. Hatsuta, K. Wakabayashi, Chem. Lett. (2000) 11081109.
T. Tago, T. Hatsuta, K. Miyajima, M. Kishida, S. Tashiro, K. Wakabayashi, J. Am.
Ceram. Soc. 85 (2002) 21882194.
S. Takenaka, Y. Orita, H. Matsune, E. Tanabe, M. Kishida, J. Phys. Chem. C 111
(2007) 77487756.
T. Yoshida, T. Tanaka, H. Yoshida, T. Funabiki, S. Yoshida, J. Phys. Chem. 100 (1996)
23022309.
S. Takenaka, H. Ogihara, I. Yamanaka, K. Otsuka, Appl. Catal. A 217 (2001)
101110.
R.B. Greegor, F.W. Lytle, J. Catal. 63 (1980) 476486.
S.D. Jackson, J. Willis, G.D. McLellan, G. Webb, M.B.T. Keegan, R.B. Moyes, S.
Simpson, P.B. Wells, R. Whyman, J. Catal. 139 (1993) 191206.
A.S. Al-Ubaid, Ind. Eng. Chem. Res. 27 (1988) 790795.
R. Takahashi, S. Sato, T. Sodesawa, M. Yoshida, S. Tomiyama, Appl. Catal. A 273
(2004) 211215.
T. Borowiecki, Appl. Catal. 4 (1982) 223231.
O. Yamazaki, T. Nozaki, K. Omata, K. Fujimoto, Chem. Lett. (1992) 19531954.
S. Takenaka, S. Kobayashi, H. Ogihara, K. Otsuka, J. Catal. 217 (2003) 7987.
J. Rostrup-Nielsen, D.L. Trimm, J. Catal. 48 (1977) 155.
I. Alstrup, J. Catal. 109 (1988) 241251.
R.T.K. Baker, Carbon 27 (1989) 315323.
S. Takenaka, H. Ogihara, K. Ostuka, J. Catal. 208 (2002) 5463.