Catalysis Communications 12 (2010) 157–160

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Catalysis Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c a t c o m

Short Communication

Steam reforming of ethanol over metal-oxide-promoted Pt/SiO2 catalysts: Effects of

strong metal-oxide interaction (SMOI)
Shin-ichi Ito a,⁎, Keiichi Tomishige a,b
a
University of Tsukuba, Graduate School of Pure and Applied Sciences, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
b
Tohoku University, Graduate School of Engineering, Aoba 6-6-07, Aramaki, Aoba-ku, Sendai, Miyagi 980-8579, Japan

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

Article history: The steam reforming of ethanol over metal-oxide-promoted Pt/SiO2 catalysts after H2 reduction was
Received 23 June 2010 investigated. The catalysts were prepared by sequential impregnation with an aqueous solution of Pt(NO2)2
Received in revised form 13 September 2010 (NH3)2 and aqueous solutions of metal complexes of V, Nb, and Mo. For a range of low temperatures (393–513 K),
Accepted 16 September 2010
the ethanol conversion achieved by adding these metal oxides was greater than that achieved when an un-
Available online 22 September 2010
promoted-Pt/SiO2 catalyst was used. The highest ethanol conversion was achieved in the case of the Nb-oxide-
promoted Pt/SiO2 catalyst; in this case, the ethanol conversion was the highest and it was 2.7 times higher than
Keywords:
Ethanol steam reforming
that in the case of the un-promoted Pt/SiO2 catalyst at 473 K. The results of catalyst characterization suggest that
Bio-ethanol the surface of Pt metal particles was covered by NbOx. The effects of strong metal-oxide interaction (SMOI) in Pt–
Pt catalyst NbOx enhanced the steam reforming of ethanol.
SMOI © 2010 Elsevier B.V. All rights reserved.
SMSI
Hydrogen production

−1
1. Introduction CO þ H2 O→H2 þ CO2 ΔH ¼ −41:2 kJ mol water gas shift reaction ð8Þ

Hydrogen is the most important resource for producing chemical −1

2CO→CO2 þ C ΔH ¼ −172:5 kJ mol Boudouard reaction ð9Þ
materials and/or fuel for use in polymer electrolyte fuel cells (PEFCs)
[1–3]. Hydrogen can be formed by steam reforming of hydrocarbons
or methanol [4–8]. Recently, ethanol (bio-ethanol) has attracted The reaction (1) is suitable for steam reforming of ethanol, it
attention for use as a more suitable source of hydrogen than fossil involves the other reactions. Reactions (6) and (9) induce carbon
resources since it can help to reduce the emission of greenhouse gases deposition which results in catalyst deactivation. Some groups have
[9–22]. The main pathway of the steam reforming of ethanol is reported the steam reforming of ethanol over supported metal
considered to be as follows: catalysts; the catalytic performance which is determined by ethanol
conversion, selectivity towards hydrogen formation and tolerance to
−1
C2 H5 OH þ 3H2 O→6H2 þ 2CO2 ΔH ¼ þ173:8 kJ mol ð1Þ deactivation can be improved by secondary additives [10,19,22]. In
−1
the case of supported noble metal catalysts, the catalytic performance
C2 H5 OH þ H2 O→2H2 þ CH4 þ CO2 ΔH ¼ þ8:8 kJ mol ð2Þ can also be improved by the addition of metal oxides as well as
−1 secondary metals.
C2 H5 OH→H2 þ CH3 CHO ΔH ¼ þ69:0 kJ mol ð3Þ We have reported that strong metal-oxide interaction (SMOI) in
−1 SiO2-supported Rh catalysts was generated by addition of SMSI oxides
C2 H5 OH→C2 H4 þ H2 O ΔH ¼ þ45:79 kJ mol ð4Þ
such as Nb2O5 or V2O5 followed by high-temperature calcination
CH3 CHO→CH4 þ CO ΔH ¼ −19:0 kJ mol
−1
ð5Þ above 773 K. Mixed oxides (RhNbO4 or RhVO4) were produced by
high-temperature calcination. The mixed oxides were decomposed to
−1 Rh metal particles and partially reduced oxide such as NbOx by H2
C2 H4 →2H2 þ 2C ΔH ¼ −52:3 kJ mol ð6Þ
reduction at low temperature (LTR), this resulted in the SMOI. Rh
−1
CH4 þ H2 O→CO þ 3H2 ΔH ¼ þ206:2 kJ mol ð7Þ metal particles were partially covered by the NbOx. Therefore, the
amounts of H2 or CO chemisorptions were much lower than the
number of surface Rh atoms; the latter value was calculated from the
size of Rh metal particles. However, the SMOI enhanced the catalytic
⁎ Corresponding author. Tel.: + 81 29 853 5479. activity and selectivity toward C2-oxygenates (C2H5OH, CH3COOH,
E-mail address: ito@ims.tsukuba.ac.jp (S. Ito). CH3CHO and HOC2H4OH) in CO hydrogenation [23–28].

1566-7367/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2010.09.022
158 S. Ito, K. Tomishige / Catalysis Communications 12 (2010) 157–160
In this study the SMSI oxides (Nb2O5, V2O5, and MoO3) were added
to SiO2-supported Pt catalyst. We report the effects of SMOI in a SiO2-
supported Pt catalyst on the steam reforming of ethanol; we also
report the results of catalyst characterization.
2. Experimental
Catalysts were prepared by sequential impregnation with an aqueous
solution of Pt(NO2)2(NH3)2 and aqueous solutions of metal complexes of
V, Nb, and Mo [29]. A SiO2 support (Fuji Silysia Chemical Ltd., G-6, BET
surface area: 530 m2 g−1) was first impregnated with a boiling aqueous
solution of Pt(NO2)2(NH3)2 (Soekawa Chemicals Ltd.) by the incipient
wetness method. The Pt content of all catalysts was 2 wt.%. The sample
was dried in air at 383 K overnight after the first impregnation. After the
sample was dried, it was impregnated with an aqueous solution of
NH4VO3, (NH4)3[NbO(C2O4)3], or (NH4)6Mo7O24·4H2O. (NH4)3[NbO
(C2O4)3] was provided by CBMM International Ltd. and other chemicals
were provided by Wako Chemicals Ltd. The second impregnation was
also performed by the incipient wetness method. The molar ratio of metal
to Pt for all catalysts was 3. After the second impregnation, the samples
were again dried overnight in air at 383 K. Subsequently, dried samples
were calcined in air at 773 K for 3 h. All catalysts were treated in a H2
stream (30 ml min−1) at 773 K for 1 h before performing the steam
reforming of ethanol. These metal-oxide-promoted Pt/SiO2 catalysts are
denoted as V–Pt/SiO2, Nb–Pt/SiO2, and Mo–Pt/SiO2. To verify the effect of
SMOI, SiO2-supported V oxide, Nb oxide, and Mo oxide samples were also
prepared by impregnation of each precursor as the above mentioned
(without first Pt impregnation). These samples are denoted as V/SiO2,
Nb/SiO2, and Mo/SiO2.
A catalytic reaction was carried out using a fixed-bed flow reactor
system equipped with on-line TCD gas chromatographs at atmospheric
pressure [6,7]. Hundred milligrams of the catalyst was placed in a quartz
reactor. An aqueous solution of ethanol (14 wt.%) rather than real bio-
ethanol was introduced into the pre-heater as a reactant in steam
reforming by using a micro-cylinder pump; the solution was introduced
into the reactor along with Ar as a carrier gas (18.8 ml min−1). The feed
rate of the reactant was 3.0 μl min−1. The total flow rate was 22 ml min−1;
ethanol: 1 vol%, H2O: 14 vol%, and Ar: 85 vol% as the gas phase. To
evaluate the Pt metal particle size after H2 reduction, X-ray diffraction
(XRD) measurements were carried out on an X-ray diffractometer in the
presence of Cu Kα (45 kV, 40 mA) radiation. The mean size of Pt particles
(d nm) was calculated from the XRD line broadening measurement by
using the Scherrer equation [30–34]. The dispersion (D) of the Pt particles
was calculated by the following equation; D=1.135/d. It was assumed
that the Pt particle was globular, and the equation was used [33]. H2 and
CO adsorption measurements were carried out on a conventional
volumetric adsorption apparatus; detailed procedures have been pre-
sented elsewhere [35]. The amounts of irreversible H2 adsorption (H/Pt)
and irreversible CO adsorption (CO/Pt) were measured at room
temperature after O2 treatment at 773 K for 1 h followed by H2 reduction
at 773 K for 1 h. These irreversible adsorptions are referred as H2 or CO
chemisorptions.
3. Results and discussion
Fig. 1 shows the results of X-ray diffraction (XRD) measurements of
metal-oxide-promoted Pt/SiO2 and un-promoted Pt/SiO2 catalysts; the
measurements were performed after H2 reduction at 773 K. In the XRD
patterns for these catalysts, three peaks appeared around 39.7°, 46.2°,
and 67.5° (2θ), and the main peak was around 39.7°. All these peaks
were assigned to the reduced Pt metal [36]. In the case of the un-
promoted Pt/SiO2 catalyst, the peak was broad and had low intensity.
This result implies that the Pt metal particle was highly dispersed on the
SiO2 support. In the case of other catalysts, the main peak was narrower
and more intense than that due to the un-promoted Pt/SiO2 catalyst.
These results suggest that the size of the Pt particles increased because of
: Pt
Intensity / a. u.
(d)
(c)
(b)
(a)
40 50 60 70
2 θ /degree
Fig. 1. The results of X-ray diffraction (XRD) measurements of metal-oxide-promoted
and un-promoted Pt/SiO2 catalysts after H2 reduction at 773 K. (a) Pt/SiO2, (b) Nb–Pt/
SiO2, (c) V–Pt/SiO2, and (d) Mo–Pt/SiO2.
the addition of the SMSI oxides such as Nb, V, and Mo oxides. The size of
Pt particles was calculated from the X-ray line broadening measure-
ments by using the Scherrer equation [30–34] and the results are listed
in Table 1, and the dispersion based on the XRD results is also listed in
Table 1. The number of surface Pt atoms can be estimated from the
chemisorption amount of H2 and CO, which can bring the dispersion
based on the chemisorption amount as listed in Table 1. In the case of Pt/
SiO2, the dispersion from the XRD (D = 0.39) agreed well with that from
the chemisorptions (H/Pt = 0.44 and CO/Pt= 0.47). On the other hand,
in the case of metal-oxide-promoted Pt/SiO2 catalysts, the dispersion
from the chemisorption was much smaller than that from the XRD
result, indicating that the presence of metal oxide species suppresses the
chemisorption. An important point is that no peak corresponding to
metal oxides was observed in the range of 5° to 75° in the case of the
metal-oxide-promoted Pt/SiO2 catalysts (low angle side was not
shown), suggesting that the size of the metal oxides is so small that
the X-ray diffraction does not take place [34]; the size may be below
2.0 nm. As a result, these metal oxides can be highly dispersed on the
SiO2 support or on the Pt particles, and considering from the suppression
of the chemisorption by the presence of metal oxide species on Pt/SiO2,
it is suggested that the metal oxide species covers the surface of Pt metal
particles on the basis of the previous reports that metal oxide species
located on noble metal particles such as Pt and Rh cannot adsorb H2 and
CO [23–32,37–39]. It should be noted that the addition of the metal
oxides increased the size of Pt metal particles and this can be a negative
factor in terms of the catalytic activity, in fact, this negative factor is
compensated by the promoting effect of the modification with metal
oxide species as shown later. At present, the mechanism for the growth
of Pt metal crystallite is not investigated sufficiently, however, it is
suggested that the coverage of the Pt metal surface with metal oxide
species causes the aggregation of metal particles.
The state of the metal oxide species located on the Pt metal surface
is not analyzed, and further investigation is necessary especially by
temperature-programmed reduction (TPR) and spectroscopic studies.
In the catalyst preparation, after high-temperature calcination, Nb
oxide is generally the stable Nb2O5. However, in the presence of a
noble metal such as Pt and Rh, Nb2O5 can be reduced by H2 treatment
at a high temperature (773 K) as reported previously [30,31]. The
previous reports suggest that Nb oxide species is partially reduced to
Nb4+, and the Nb species is represented as NbOx because the chemical
state of Nb species is not determined. In the case of V–Pt/SiO2 and
Mo–Pt/SiO2 catalysts, a similar decrease in the amounts of H2 or CO
chemisorption was also observed. In these catalysts, the V oxide or Mo
oxide may be partially reduced, and the Pt metal particles may be
 S. Ito, K. Tomishige / Catalysis Communications 12 (2010) 157–160 159

Table 1
The results of XRD measurements and irreversible H2 and CO adsorptions (chemisorptions) measurements of the metal-oxide-promoted and un-promoted Pt/SiO2 catalysts after H2
reduction at 773 K.

Catalystsa) XRD Chemisorptiond)

Particle size (d)/nmb) Dispersion (D)c) H/Pt ((H/Pt)/D) CO/Pt ((CO/Pt)/D)

Pt/SiO2 2.9 0.39 0.44 (1.1) 0.47 (1.2)

Nb–Pt/SiO2 5.7 0.20 0.03 (0.15) 0.03 (0.15)
V–Pt/SiO2 16.9 0.07 0.03 (0.43) 0.09 (1.3)
Mo–Pt/SiO2 19.7 0.06 0.01 (0.17) 0.02 (0.33)
a)
M/Pt = 3.
b)
Calculated from the Scherrer equation.
c)
D = 1.135/d.
d)
Calculated from irreversible adsorption.

covered by the respective species [26,38,40]. The ratio of chemisorp-
tion amount (H/Pt or CO/Pt) to the dispersion (D) determined from
XRD is also listed in Table 1, and the ratio represents the amount of
surface Pt atoms without being covered with metal oxide. For the un-
promoted Pt/SiO2 catalyst, the ratios were approximately 1, namely,
the dispersion (D) agreed well with the H/Pt or CO/Pt. On the other
hand, for the Nb–Pt/SiO2 catalyst, the values ((H/Pt)/D or (CO/Pt)D)
were so decreased. This result suggests that most of the surface of Pt
metal particles were covered by NbOx species. The V–Pt/SiO2 and Mo–
Pt/SiO2 catalysts also exhibited similar results. These results indicate
the occurrence of the SMOI over the metal-oxide-promoted Pt/SiO2
catalysts.
Fig. 2 shows the dependence of ethanol conversion over the various
metal-oxide-promoted Pt/SiO2 (M/Pt = 3) catalysts and ethanol con-
version over the un-promoted Pt/SiO2 catalyst on reaction temperature.
In the case of the un-promoted Pt/SiO2 catalyst, ethanol conversion
increased at around 413 K and reached 100% at 553 K. On the other
hand, metal-oxide-promoted Pt/SiO2 catalysts exhibited higher activity
than the un-promoted Pt/SiO2 catalyst. The Nb–Pt/SiO2 catalyst showed
the highest activity among the metal-oxide-promoted Pt/SiO2 catalysts;
in the case of this catalyst, the ethanol conversion increased at around
393 K and reached 100% at 513 K. In addition, it was found that the Nb/
SiO2, V/SiO2, and Mo/SiO2 showed no catalytic activity in the
temperature range of 393–573 K. This indicates that the SMOI effect
enhanced the catalytic activity for the steam reforming of ethanol. The
V–Pt/SiO2 catalyst exhibited almost the same activity as the Nb–Pt/SiO2
catalyst; this activity was higher than that of the un-promoted Pt/SiO2
catalyst; and was lower than that of the Nb–Pt/SiO2 catalyst in the
temperature range 453–513 K. This also indicates the effect of the SMOI.
100
80
Ethanol conversion / %
In the case of the Mo–Pt/SiO2 catalyst, ethanol conversion was greater
than that in the case of the un-promoted Pt/SiO2 catalyst up to 513 K.
However, the ethanol conversion did not increase significantly above
513 K.
The product distribution in steam reforming of ethanol over the
metal-oxide-promoted Pt/SiO2 and the un-promoted Pt/SiO2 cata-
lysts at 473 K is listed in Table 2. The order of ethanol conversion at
473 K was as follows: Nb–Pt/SiO2 N V–Pt/SiO2 N Mo–Pt/SiO2 N Pt/SiO2.
The Nb–Pt/SiO2 catalyst exhibited the highest conversion and H2
formation rate among all the catalysts. In the case of the un-promoted
Pt/SiO2 catalyst, the main products were H2, CO2, and CH4. The H2:
CO2:CH4 molar ratio was approximately 2:1:1. This steam reforming
of ethanol over the un-promoted Pt/SiO2 catalyst seems to proceed by
reaction (2) (see Introduction). It was concluded that the dehydration
of ethanol (reaction (4)) also occurred since a small amount of C2H4
was detected. On the other hand, in the case of the Nb–Pt/SiO2
catalyst, the main products were H2, CO, CH4, and CH3CHO; and trace
level of CO2 was detected. This result was significantly different from
that in the case of the un-promoted Pt/SiO2 catalyst. This indicates
that the reaction pathway or rate of each reaction process is different
for these catalysts. In the case of the Nb–Pt/SiO2 catalyst, dehydro-
genation of ethanol rapidly occurred. However, the rate of reforming
or decomposition of CH3CHO was not so fast; but a small amount of
CH3CHO was decomposed to CO and CH4. On the other hand, in the
case of the un-promoted Pt/SiO2 catalyst, the rate of dehydrogenation
of C2H5OH was not so fast compared with that in the case of the Nb–
Pt/SiO2 catalyst. However, the rate of decomposition of CH3CHO and
following water gas shift reaction rapidly occurred. We also tested
steam reforming of ethanol over the Nb–Pt/SiO2 catalyst of which the
space velocity of the reactant was 3.3 times compared with the other
reaction. Although the ethanol conversion was the same level (30%),
H2 formation rate was higher than that in the case of the un-promoted
Pt/SiO2 catalyst. The details will be examined in the future. In the case
of the V–Pt/SiO2 and Mo–Pt/SiO2 catalysts, the main products were
H2, CO, CH4, and CH3CHO; the product distribution was the similar to

the case of the Nb–Pt/SiO2 catalyst. However, for the Mo–Pt/SiO2

catalyst, carbon deposition may have occurred because of the
60 suppression of ethanol conversion at higher temperatures (see
Fig. 2). In the case of the Nb–Pt/SiO2 catalyst, no deactivation was
observed after 10 h in the stream at 473 K.
40
In the steam reforming of ethanol, the metal-oxide-promoted Pt/
SiO2 catalysts exhibited higher activity than the un-promoted Pt/SiO2
20 catalyst. In particular, in the case of the Nb-oxide-promoted Pt/SiO2
catalyst, the SMOI effect enhanced the catalytic performance for the
reaction. More detailed investigations must be carried out.
0
400 450 500 550
Temperature / K Acknowledgements

Fig. 2. The dependence of ethanol conversion over the various metal-oxide-promoted

Pt/SiO2 catalysts and ethanol conversion over the un-promoted Pt/SiO2 catalyst on
This work was supported by the Grant-in-Aid for Scientific Research
reaction temperature. ■: Nb–Pt/SiO2, □: Nb/SiO2, ▽: V–Pt/SiO2, ▼: V/SiO2, ●: Mo–Pt/ (22915008). We also thank Prof. Kimio Kunimori (University of
SiO2, ○: Mo/SiO2, and △: Pt/SiO2. Tsukuba) for helpful discussions.
160 S. Ito, K. Tomishige / Catalysis Communications 12 (2010) 157–160

Table 2
The comparison of the ethanol conversion, H2 formation rate and product distributions for the steam reforming of ethanol over the metal-oxide-promoted Pt/SiO2 and un-promoted
Pt/SiO2 catalysts at 473 K.

Catalysts Ethanol conversion/%a) H2 formation rate/ Product distribution/%

10−6 mol min−1
H2 CO CO2 CH4 C2H4 C2H6 CH3CHO

Pt/SiO2 30 2.5 43 0 27 25 5 0 0
Nb–Pt/SiO2 80 7.4 42 11 trace 14 0 0 33
Nb–Pt/SiO2b) 30 4.2 40 6 3 11 0 0 40
V–Pt/SiO2 69 6.2 44 8 0 8 0 0 40
Mo–Pt/SiO2 51 4.1 45 4 0 6 0 0 45
a)
Ethanol feed rate: 8.85 × 10− 6 mol min− 1.
b)
Ethanol feed rate: 1.48 × 10− 5 mol min− 1, the reactant gas composition was the same as the other reactions, catalyst: 50 mg.

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