Applied Catalysis A: General 261 (2004) 211219

n-Pentane isomerization over platinum-promoted W/Zr mixed

oxides supported on mesoporous silica
Tao Li, She-Tin Wong, Man-Chien Chao, Hong-Ping Lin, Chung-Yuan Mou, Soofin Cheng
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan
Received 20 May 2003; received in revised form 9 October 2003; accepted 8 November 2003

Abstract
W/Zr mixed oxides supported on various porous silica materials, namely SBA-15, MCM-41 and silica gel, were prepared. Their acidities
and catalytic activities in n-pentane isomerization were examined. For the mesoporous silica, SBA-15 was found to retain the ordered
meso-structure better than MCM-41 after loading with W/Zr mixed oxide. TEM photographs showed that tungstated zirconia was dispersed
inside the mesoporous channels of SBA-15, and that the surface area and pore volume decreased with the loading. The SBA-15 supported
WO3 /ZrO2 materials promoted with Pt were highly catalytic efficient in n-pentane isomerization with a very high iso-pentane selectivity. In
contrast, MCM-41 and silica gel supported WO3 /ZrO2 showed lower catalytic activities. The optimal activity was observed on SBA-15 with
1%Pt/20%WO3 /40%ZrO2 . The mesoporous silica supports played an important role in stabilizing the mixed oxide catalyst since the catalytic
activity decayed less markedly with time-on-stream on the supported catalysts.
2003 Elsevier B.V. All rights reserved.
Keywords: Tungstated zirconia; Mixed oxide; Catalyst; Acid; Mesoporous silica; MCM-41; SBA-15; Isomerization of n-pentane; Platinum

1. Introduction
Since the discovery of mesoporous molecular sieves of
M41S family by a Mobil research group [1], many mesoporous solids with controlled pore sizes and morphologies
have been synthesized [2]. They are considered to be potential catalysts or catalyst supports due to their high thermal stability (up to 800 C), uniformly arranged mesopores
and very high surface areas (ca. 1000 m2 /g). However, in
spite of having larger pore dimensions, the acidity of mesoporous materials like Al-MCM-41 is much weaker than
that of microporous zeolites [3]. In order to overcome this
drawback, a great effort has been focused on introducing
strong acid sites on the mesoporous materials. Some hybrid
inorganicorganic mesoporous materials with alkylsulfonic
acid groups were synthesized. They were reported to behave
as strong acid catalysts in the condensation reactions and
also in the esterification reactions [48]. The hybrid materials, however, cannot be applied to systems where reaction

Corresponding author. Tel.: +886-2-2363-8017;

fax: +886-2-2363-6359.
E-mail address: chem1031@ccms.ntu.edu.tw (S. Cheng).

0926-860X/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2003.11.006

temperature is higher than ca. 250 C due to the low thermal

stability of the organic component.
In the effort to develop environmentally friendly strong
solid acids to replace the hazardous mineral acids, such as
HF and H2 SO4 commonly employed in todays petrochemical industry, sulfated zirconia (SZ) has attracted great attention in the past decade because it demonstrated high catalytic
activities in skeletal isomerization of alkanes at relatively
low temperatures [911]. Over the past few years, several
ways of supporting SZ on MCM-41 have been reported
[1216]. The resultant materials were found to be very active in MTBE synthesis and skeletal isomerization of alkane.
However, serious concerns remain about the long-term stability of SZ in reducing and oxidizing environments typically
encountered in hydrocarbon reactions and catalyst regeneration due to the gradual loss of sulfur. Hino and Arata [17,18]
found that zirconia loaded with tungsten oxide (abbreviated
as WZ) or molybdenum oxide (abbreviated as MoZ) also
showed high catalytic activities in strong acid catalyzed
reactions. Very recently, we successfully supported Mo/Zr
mixed oxide on MCM-41. Such materials were excellent
in catalyzing liquid phase condensation of 2-methylfuran
with acetone to form 2,2-bis(5-methylfuryl)propane [19].
Although zirconia loaded with tungsten oxide was also

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T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

reported to be a strong acid catalyst [17], up to now, no reports have described mesoporous materials supported with
these mixed oxides. The aims of this study are to introduce
acid function onto the mesoporous materials by supporting
W/Zr mixed oxide on them and to examine the catalytic activities of the resultant materials in n-pentane isomerization.

2. Experimental section
2.1. Catalyst preparation
Pure siliceous MCM-41 was synthesized according to
the method reported by Das et al. [20]. The molar ratio of
the synthesis gel composition is SiO2 :0.48 CTMA+ :0.33
TPA+ :0.39 Na2 O:0.29 H2 SO4 :110 H2 O. Pure siliceous
SBA-15 was synthesized according to the method reported
by Kao et al. [21]. The gel chemical composition in molar ratio was P123:60 TEOS:1506 HCl:9706 H2 O. The
as-synthesized mesoporous samples were calcined in air at
560 C for 6 h to remove the organic surfactant templates.
The W/Zr mixed oxides were supported on various silica
materials by co-impregnation of zirconium(IV) acetylacetonate and ammonium metatungstate hydrate. The silica materials such as MCM-41, SBA-15 and SiO2 gel (Aldrich), in
powder form were dispersed in a methanol solution of zirconium(IV) acetylacetonate (Aldrich) under vigorous stirring.
Then aqueous ammonium metatungstate hydrate (Aldrich)
was added and the stirring was continued for about 1 h. After the solvent was removed with a rotary evaporator, the
solid was dried in air overnight at 110 C. Most of the dried
samples were calcined in air at 800 C for 3 h except those
mentioned separately. The resultant calcined samples were
impregnated with platinum tetrachloride (Janssen) solution
and dried overnight at 110 C. This process was followed
by calcination in air at 500 C for 3 h. W/Zr mixed oxides
without support were also prepared by mixing a methanol
solution of zirconium(IV) acetylacetonate and aqueous ammonium metatungstate hydrate under vigorous stirring; then
the same treatments as for supported samples were followed.

from 120 to 800 C at a heating rate of 10 C/min. The

desorption process was monitored by a quadruple mass
spectrometer (Thermo ONIX, ProLab) connected on-line
through a heated capillary interface. The mass number 16
was followed to obtain TPD profiles of NH3 because this
mass intensity is relatively strong and the interference from
H2 O is negligible.
Diffuse reflectance infrared Fourier transform (DRIFT)
spectra of the samples that adsorb pyridine were recorded
using a BOMEM MB155 FT-IR/Raman spectrometer. The
equipment was furnished with an in situ sample cell (Harrick). The sample was pre-heated at 300 C for 3 h under
106 mbar vacuum before pyridine vapor was introduced at
room temperature; this process was followed by evacuation
for 30 min. Spectra were acquired from room temperature
to 500 C under vacuum.
The temperature-programmed oxidation (TPO) was carried out on a Du Pont 951 thermogravimetric analyzer. The
heating rate was 10 C/min and the carrier gas was dried air
with a 60 ml/min flow rate.
2.3. Catalytic study
The catalytic reaction of n-pentane isomerization was carried out in a fixed-bed micro-reactor at atmospheric pressure.
A 0.5 g portion of the catalyst was packed into the reactor
and then pretreated in dried air at 450 C for 3 h. The reactor temperature was then lowered to the reaction temperature of 250 C under a flow of N2 . The reaction feed was a
mixture of n-pentane, hydrogen and nitrogen with the flow
rates of 0.62, 2, and 10 ml/min, respectively. The reaction
feed flowed through the catalyst bed at an n-pentane weight
hourly space velocity (WHSV) of 0.24 h1 . The reaction
products were analyzed on-line with a Shimadzu GC-14A
gas chromatograph, equipped with a FID and capillary column (RTX-1, 60 m). Regeneration of the used catalyst was
carried out in situ under flowing air at 450 C for 3 h.

3. Results and discussion

2.2. Catalyst characterization

3.1. Characterization of catalysts

Low-angle powder X-ray diffraction (XRD) patterns

were taken on the Wiggler-A beamline ( = 0.1326 nm)
of the National Synchrotron Radiation Research Center,
Hsinchu, Taiwan. Mid-angle patterns were recorded with a
Scintag X1 diffractometer using Cu K radiation. Nitrogen
adsorption-desorption isotherms were obtained at liquid
nitrogen temperature with a Micromeritics ASAP 2000
apparatus. Transmission electron microscopy (HRTEM)
was performed on a Philips Tecnai FEG-TEM instrument
operated at 200 kV.
The temperature-programmed desorption of ammonia
(NH3 -TPD) was carried out on a Micromeritics AutoChem
2910 instrument. TPD profiles of ammonia were obtained

Fig. 1A shows the XRD patterns of pure SBA-15 and

the 1%Pt/WO3 /ZrO2 /SBA-15 samples with the WO3 /ZrO2
weight ratio kept constant at 0.50 while the ZrO2 /SBA-15
weight ratios varied. In the small-angle region, the three distinct diffraction peaks correspond to the 100, 110, 200 reflections of SBA-15. The well resolved hexagonal structure
of SBA-15 was retained even when the ZrO2 /SBA-15 weight
ratio was as high as 0.54. When the ZrO2 /SBA-15 weight
ratio is further increased, the 110 and 200 reflections disappear, and the intensity of the 100 diffraction peak decreases
drastically. This might be due to the decrease in diffraction contrast after filling the mesoporous channels with the
mixed oxides.

T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

213

Fig. 1. XRD patterns of (a) SBA-15 and the 1%Pt/WO3 /ZrO2 /SBA-15 samples with (A) 0.50 weight ratio of WO3 /ZrO2 and different ZrO2 /SBA-15
weight ratios of (b) 0.10; (c) 0.25; (d) 0.54; (e) 1.0; and (f) 1.86. (B) 1.0 weight ratio of ZrO2 /SBA-15 and different WO3 /ZrO2 weight ratios (b) 0.20;
(c) 0.35; (d) 0.50; and (e) 0.65.

No diffraction peaks corresponding to either ZrO2 or WO3

crystallites were observed in the wide-angle region for samples with WO3 /ZrO2 weight ratio of 0.50 and ZrO2 /SBA-15
weight ratio lower than 0.25. Therefore, ZrO2 and WO3 below these loadings should be well dispersed on the surface
of SBA-15. As the ZrO2 /SBA-15 weight ratio is over 0.54,
tetragonal ZrO2 phase was observed. Furthermore, monoclinic ZrO2 phase also appeared when the ZrO2 /SBA-15
ratios were higher than 1.0. On the other hand, no peaks
corresponding to WO3 crystallites could be seen until the
ZrO2 /SBA-15 ratio was raised to 1.0. In comparison of
the two mesoporous silica samples of hexagonal structure,
SBA-15 seemed to keep its ordered porous structure better
than MCM-41 after supporting W/Zr mixed oxides, since
MCM-41 lost its hexagonal diffraction peaks completely after supporting similar amounts of W/Zr mixed oxide. Therefore, most studies hereafter were focused on the SBA-15
supported samples.
Fig. 1B shows the XRD patterns of 1%Pt/WO3 /ZrO2 /
SBA-15 samples with constant ZrO2 /SBA-15 weight ratio of
1.0 and different WO3 /ZrO2 weight ratios. In the small-angle
region, the diffraction peaks of SBA-15 were relatively low
for samples supported with W/Zr mixed oxides, because
of the high loading of ZrO2 . In the wide-angle region the
situation is similar to that in Fig. 1(a). When the WO3 /ZrO2
weight ratio increased to 0.50, small peaks corresponding to
WO3 phase began to appear. At the same time, monoclinic
ZrO2 phase appeared in addition to the tetragonal phase.
The latter was the only phase observed when the WO3 /ZrO2
weight ratio was lower than 0.50.

The physical properties measured from nitrogen adsorption-desorption isotherms of various porous silica materials
and those supported with W/Zr mixed oxide are tabulated in
Table 1. The parent SBA-15 sample calcined at 560 C has a
BET surface area of 636 m2 /g, a pore volume of 0.86 cm3 /g
and a pore size distribution centered at 8.4 nm. After supporting tungstated zirconia on it, the BET surface area and
pore volume were found to decrease with the increase in
oxide loading. Since all the SBA-15 supported mixed oxide samples were calcined at 800 C, a parent SBA-15 sample calcined at such a high temperature was also studied.
The surface area, pore volume and pore diameter decrease
to 452 m2 /g, 0.62 cm3 /g and 7.5 nm, respectively. Relative
to this high temperature calcined parent sample, the surface
area and pore volume of the SBA-15 sample loaded with
WO3 /ZrO2 did not decrease so significantly, implying that
the supported oxide should be dispersed onto the internal
surfaces of the mesopores of SBA-15. The HRTEM photograph of 20%WO3 /40%ZrO2 /SBA-15 shown in Fig. 2 confirmed that the hexagonally arranged mesopores of SBA-15
were retained and that WZ was mainly dispersed inside the
pores.
A comparison of the three different silica materials supporting with the same amount of WZ (20%WO3 /40%ZrO2 )
showed that the surface areas were close: 137, 162 and
141 m2 /g for SBA-15, MCM-41 and silica gel, respectively.
However, the differences in pore volume were marked: 0.21,
0.11 and 0.17 cm3 /g, respectively. The relatively lower pore
volume on MCM-41 supported sample implies that WZ particles may seriously block its mesopores, but such blocking

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T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

Table 1
Physical properties of porous silica-supported mixed oxide catalysts
Sample

WO3 /ZrO2
(weight ratio)

ZrO2 /support
(weight ratio)

Calcination
temperature ( C)

BET area
(m2 /g)

BJH pore
volume (cm3 /g)

Pore diameter
(nm)

SBA-15
SBA-15
4.3%WO3 /8.6%ZrO2 /SBA-15
9.1%WO3 /18%ZrO2 /SBA-15
15%WO3 /30%ZrO2 /SBA-15
20%WO3 /40%ZrO2 /SBA-15
24%WO3 /49%ZrO2 /SBA-15
9.1%WO3 /45%ZrO2 /SBA-15
15%WO3 /43%ZrO2 /SBA-15
24%WO3 /38%ZrO2 /SBA-15
SiO2 gel
20%WO3 /40%ZrO2 /SiO2
17%WO3 /ZrO2
MCM-41
20%WO3 /40%ZrO2 /MCM-41
S-50%ZrO2 /MCM-41

0.50
0.50
0.50
0.50
0.50
0.20
0.35
0.65

0.50
0.20

0.50

0.10
0.25
0.54
1.0
1.86
1.0
1.0
1.0

1.0

1.0
1.0

560
800
800
800
800
800
800
800
800
800
560
800
800
560
800
680

636
452
411
301
201
137
92
216
166
125
660
141
24
1085
162
476

0.86
0.62
0.60
0.42
0.30
0.21
0.14
0.25
0.22
0.20
0.67
0.17
0.03
1.0
0.11
0.41

8.4
7.5
8.0
7.0
6.8
6.2
6.2
6.3
5.8
6.9

2.7
2.1
2.5

is less significant on SBA-15 support of relatively larger pore

diameter. On the other hand, the supported catalysts have
much larger surface areas than the unsupported WO3 /ZrO2
(24 m2 /g).
The temperature-programmed desorption of ammonia
(NH3 -TPD) was performed to determine the amount and
strength of acid sites on the catalysts. The presence of Pt
promoter on the samples did not change the TPD profiles.
Therefore, only the profiles of the samples with Pt promoter
are shown. Fig. 3A compares the NH3 -TPD profiles of WZ
samples supported on various silica supports with those of
the unsupported WZ and of the sulfated ZrO2 supported on
MCM-41. The WZ loading in the three supported samples
remained the same: 20%WO3 and 40%ZrO2 . For the unsupported WZ, the 17%WO3 /ZrO2 was the one showing the

Fig. 2. HRTEM photograph of 1%Pt/20%WO3 /40%ZrO2 /SBA-15 sample.

highest catalytic activity in n-pentane isomerization. All the

samples gave a broad desorption band covering 150500 C
and centered at ca. 250 C, implying that the acid strength
of these samples was similar and in the medium strength
region. Based on the peak area, it can be concluded that WZ
supported on either SBA-15 and MCM-41 contained more
acid sites than that supported on silica gel. Furthermore, the
supported WZ samples contained many more acid sites than
the unsupported WZ. These results in union with the BET
surface area studies suggest that WZ on the meso-porous
silica supports should be highly dispersed so that a large
number of acid sites was generated. On the other hand,
MCM-41 supported sulfated ZrO2 contained even more and
stronger acid sites, which was revealed by the presence of
a shoulder at ca. 320 C on the NH3 -TPD profile.
Fig. 3B compares the NH3 -TPD profiles of SBA-15 supported WZ samples with different WO3 and ZrO2 loadings.
No direct correlation was found between the acid amount and
the oxide loading. However, samples with relatively lower
WO3 and ZrO2 contents (profiles a, b and c) contained more
acid sites than those with higher WO3 and ZrO2 contents
(profiles d and e), although the acid strength was similar.
Since the higher loading samples have lower surface area,
these results imply that good dispersion of mixed oxide on
SBA-15 is necessary in order to generate a large number of
acid sites.
The DRIFT spectra of pyridine adsorbed on WO3 /ZrO2 /
SBA-15 were taken to study the nature of the acid sites.
Fig. 4 shows the DRIFT spectra of 1%Pt/20%WO3 /
40%ZrO2 /SBA-15 sample after adsorption of pyridine and
desorption at various temperatures. It can be seen that both
Lewis (characteristic at 1450, 1487 and 1609 cm1 ) and
Brnsted (characteristic at ca. 1550 cm1 ) acidic sites are
present on the sample [14,22]. In addition, two peaks corresponding to the H-bonded pyridine appeared at 1446 and
1597 cm1 ; these disappeared after heating the sample at

T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

215

(B)

Intensity (a.u.)

(A)

(a)
(a)
(b)
(b)
(c)
(c)
(d)

(d)
(e)

200

300

400

500

600

700

(e)

800

200

300

400

500

600

700

800

Temperature ( C)
Fig. 3. NH3 -TPD profiles of (A): (a) 1%Pt/50%S-ZrO2 /MCM-41 and 1%Pt/20%WO3 /40%ZrO2 on various supports; (b) SBA-15; (c) MCM-41; (d) silica
gel; and (e) 1%Pt/17%WO3 /ZrO2 . (B) 1%Pt/WO3 /ZrO2 /SBA-15 with different WO3 and ZrO2 contents: (a) 9.1 and 18%; (b) 9.1 and 45%; (c) 20 and
40%; (d) 24 and 49%; and (e) 24 and 38%.

200 C. Judging from the area ratio, one can conclude that
the number of Lewis acidic sites was greater than that of
Brnsted ones. With the increase in desorption temperature,
the intensities of the characteristic peaks of both Lewis and
Brnsted acid sites decrease. The strength of Lewis acidic

LS

3.2. Catalytic studies

The catalytic properties of SBA-15 supported WO3 /ZrO2
were investigated in the isomerization of n-pentane to
iso-pentane. Introducing a small amount of Pt (0.5 wt.%)
onto the WZ catalyst was found to cause a great increase
in both the conversion of n-pentane and selectivity to
iso-pentane. Table 2 shows the effect of Pt loading on
n-pentane isomerization over 20%WO3 /40%ZrO2 /SBA-15
catalyst. On the Pt-free sample, only trace activity was observed. The catalytic activity, however, increases markedly
with the loading of 0.5% Pt. As the Pt loading increased

Absorbance (a.u.)

BS
(a)
(b)
(c)
(d)
(e)

Table 2
Isomerization of n-pentane over Pt/20%WO3 /40%ZrO2 /SBA-15 catalyst
with different Pt loadings

(f)

1400

sites was stronger than that of Brnsted ones since the former peak still retained some intensity up to 500 C whereas
that of the latter was completely removed. The preservation
of the pyridine peaks up to 500 C implies that the strength
of the Lewis acid sites on this supported WZ sample is
relatively strong.

1500

1600

1700

1800

-1

Wavenumber (cm )
Fig. 4. In situ DRIFT spectra of pyridine adsorbed on 1%Pt/20%WO3 /
40%ZrO2 /SBA-15. Spectra recorded after evacuating at (a) 25 C; (b)
100 C; (c) 200 C; (d) 300 C; (e) 400 C and (f) 500 C.

Pt loading
(wt.%)

n-Pentane
conversion (%)

iso-Pentane
selectivity (%)

0
0.5
1
2

0.8
54
58
61

85
99
99
97

Data obtained after 6 h on feed.

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T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

Table 3
Isomerization of n-pentane over various catalysts

70

Conversion of n-pentane (%)

60

Catalyst

n-Pentane
conversion (%)

iso-Pentane
selectivity (%)

17%WO3 /ZrO2
1%Pt/17%WO3 /ZrO2
20%WO3 /40%ZrO2 /SBA-15
1%Pt/20%WO3 /40%ZrO2 /SBA-15
1%Pt/SBA-15
2%Pt/SBA-15 + 17%WO3 /ZrO2

1.5
52
0.8
60
1.4
47

83
98
85
98
41
98

Data obtained after 6 h on feed.

50

40

30

20
700

750

800

850
o

Calcination temperature ( C)
Fig. 5. Catalytic activities of 1%Pt/20%WO3 /40%ZrO2 /SBA-15 catalyst
with the supported mixed oxide calcined at various temperatures.

from 0.5 to 2%, the n-pentane conversion increased from 54

to 61% while the iso-pentane selectivity remained around
9799%. The main by-products were from the cracking
reaction, including methane, ethane, propane, n-butane and
iso-butane. Because the change in catalytic activities for the
catalysts with Pt loading higher than 1 wt.% was negligible,
1%Pt loading was used for most of the catalytic studies
hereafter.
Fig. 5 shows the dependence of n-pentane conversion on
the calcination temperature of 20%WO3 /40%ZrO2 /SBA-15
sample. An optimal activity was observed on the catalyst
calcined at 800 C. This result is consistent with those reported by other researchers on the unsupported WZ catalysts
in isomerization of light paraffin (C4 C6 ) [2327]. On the
other hand, the iso-pentane selectivity is independent of the
calcination temperature and always has a value over 95%.
Table 3 demonstrates the effects of WZ mixed oxide and
the SBA-15 support. It can be seen that both unsupported
and SBA-15 supported WZ catalysts without Pt showed
nearly no catalytic activity in n-pentane isomerization. By
introducing 1 wt.% Pt, very high catalytic activities were
obtained on both samples. Obviously, Pt is one of the main
components contributing to the catalytic activity. However,
if only Pt is loaded onto SBA-15 without W/Zr mixed ox-

ide, n-pentane conversion was extremely low and cracking

products were the main products. Therefore, W/Zr mixed
oxide is also needed in order to obtain high catalytic activity
in n-pentane isomerization. In order to understand the contribution of Pt and WZ in acidity, a sample of 2%Pt/SBA-15
and 17% WO3 /ZrO2 was mechanically mixed in 1:1 ratio,
which contains the same amount of Pt and ZrO2 as that of
sample 1%Pt/20%WO3 /40%ZrO2 /SBA-15; this was used
as the catalyst. This sample gave similar catalytic activity to
that of the unsupported 1%Pt/WZ, but was less active than
the SBA-15 supported catalyst. This means that Pt need not
have close contact with WZ in order to catalyze n-pentane
isomerization. Tomishige et al. [28] studied n-butane isomerization over Pt-promoted sulfated zirconia. They also
found that the proximity of Pt and the acid site is not
important.
Noble metals are considered very efficient in activation of
hydrogen and suppressing the coke formation in hydrocarbon treatment processes over dual function catalysts [29,30].
The noble metals are proposed to activate hydrogen and
spillover hydrogen to the acidic sites. Without noble metals,
the catalyst usually loses its activity due to severe coking on
the acidic sites. Under our reaction conditions, all the used
catalysts were light grey in color. The TPO (temperature programmed oxidation) results showed that less than 0.5 wt.%
coke was formed on all the catalysts after n-pentane isomerization reaction for 20 h. Moreover, the Pt-free samples did
not contain much more coke. Therefore, the very low activity on Pt-free catalysts was not due to coke formation and
fouling on the active sites.
Many studies on alkane isomerization catalyzed by Ptpromoted SZ and WZ have suggested a reaction mechanism
involving spillover hydrogen [31,32]. The spilt-over H
species are supplied to the carbenium reaction intermediate,
which then desorbs as alkane product, and the spilt-over H+
species generate Brnsted acidic sites [33]. The hydrogen
spillover mechanism is different from the dehydrogenationhydrogenation mechanism in that carbenium ion instead of
alkene is the intermediate [31]. Since coke, which is easily formed from alkene, is negligible and the proximity of
Pt and the acid site is not important, the spillover mechanism is more applicable to our system. The NH3 -TPD
results suggested that introducing Pt onto the supported
and unsupported WZ samples did not increase the number

T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

80

217

ZrO2(t)

60
(a)

50

WO3

(b)

40
(c)

30
20

(d)
(e)

10

Relative Intensity

Conversion of n-pentane (%)

70

(a)

(b)
0
0

10

15

20

(m) (m)

TOS (h)
Fig. 6. Conversion of n-pentane versus time-on-stream over different catalysts promoted with 1%Pt: (a) 20%WO3 /40%ZrO2 /SBA-15; (b)
17%WO3 /ZrO2 ; (c) 50%S-ZrO2 /MCM-41; (d) 20%WO3 /40%ZrO2 /
MCM-41 and (e) 20%WO3 /40%ZrO2 /SiO2 .

(c)

20

30

40

50

60

70

2 theta (degree)
of acid sites nor the acid strength. When the Pt-promoted
WZ samples were pretreated with H2 flow at a reaction
temperature of 250 C for 2 h before the NH3 -TPD experiment, the TPD profile showed no noticeable changes either.
These results imply that the acidity of the catalyst is not
enhanced by the presence of Pt nor in combination of H2
atmosphere. In other words, the NH3 -TPD experiment did
not detect any stronger acidic sites generated by the spiltover H+ species. It is therefore suspected that the carbenium
intermediate, which is generated during the isomerization
reaction and proposed to accept spilt-over H species,
should induce the formation of strong Brnsted acidic sites
by releasing the spilt-over H+ species from the adsorbed
hydrogen.
Fig. 6 compares the catalytic activities in n-pentane isomerization of Pt-promoted WZ mixed oxide supported on
SBA-15, MCM-41 and silica gel. SBA-15 support gave the
highest n-pentane conversion. In contrast, MCM-41 and silica gel supports gave relatively low conversions. The BET
surface areas of these three supported catalysts were in
a close range of 140160 m2 /g, but the BJH pore diameter of SBA-15 catalyst was ca. 6 nm and much larger than
the 2 nm of MCM-41. Moreover, the pore volume of the
MCM-41 supported WZ catalyst was only about half of that
of the SBA-15 catalyst. Therefore, the easier diffusion of
the gaseous reactants and products in SBA-15 probably accounts for its higher activity. On the other hand, the low
catalytic activity of silica gel-supported catalyst is probably
due to the low content of tetragonal ZrO2 crystalline phase.

Fig. 7. XRD patterns of 1%Pt/20%WO3 /40%ZrO2 supported on different

silica supports: (a) MCM-41; (b) SBA-15 and (c) silica gel.

Fig. 7 compares the XRD patterns of WZ catalysts on the

three silica supports. SBA-15 supported catalyst contains
primarily tetragonal ZrO2 phase of highly crystalline form,
while silica gel-supported catalyst contains relatively small
amount of crystalline ZrO2 with both tetragonal and monoclinic phases. These results are consistent with the proposals
in many publications that tetragonal ZrO2 phase is the active
phase for acid-catalyzed reactions. The MCM-41 supported
sulfated zirconia gave very high initial activity, but it decayed rapidly with time-on stream. Thus the acidic strength
of supported sulfated zirconia is much stronger than that of
W/Zr mixed oxide; this leads to severe coking as the reaction prolongs.
The unsupported WZ gave conversion similar to that over
SBA-15 supported WZ catalyst. However, the unsupported
catalyst decays with time-on-stream faster than the supported ones. These results imply that the supports play a
role in stabilizing the catalytic active centers. On the other
hand, because NH3 -TPD experiments showed that unsupported WZ has very low acid amount (Fig. 3A), the Brnsted
acidic sites generated by the spilt-over H+ species during
the isomerization reaction should play an important role in
catalyzing the reaction.
Fig. 8 compares the catalytic performance of 1%Pt/WZ/
SBA-15 samples with different WO3 and ZrO2 contents.
It can be seen that the catalysts containing WO3 = 9.1%

218

T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

(A)

70

(a)

Conversion of n-pentane (%)

60

(B)

70

(a)

60

(b)

(b)

50

50
(c)
(c)

40

40

30

30

20

20

10

10
(d)

(d)

(e)

TOS (h)
Fig. 8. Conversion of n-pentane versus time-on-stream over 1%Pt/WZ/SBA-15 with (A) 0.50 weight ratio of WO3 /ZrO2 and different ZrO2 /SBA-15
weight ratios of (a) 1.0; (b) 1.86; (c) 0.54; (d) 0.25 and (e) 0.10. (B) 1.0 weight ratio of ZrO2 /SBA-15 and different WO3 /ZrO2 weight ratios (a) 0.50;
(b) 0.65; (c) 0.35 and (d) 0.20.

100

100

90

90
run 1
run 2
run 3

80

80

70

70

60

60

50

50

Selectivity to iso-pentane (%)

in order to generate efficient catalytic sites for n-pentane

isomerization.
The 1%Pt/20%WO3 /40%ZrO2 /SBA-15 catalyst used in
the n-pentane isomerization was recycled three times in order to examine the deactivation and regeneration behavior of
the catalyst. The results of these experiments are shown in
Fig. 9. The catalyst after 20 h reaction at 250 C was able to
recover its activity completely after it was treated in flowing
air at 450 C for 3 h.

Conversion of n-pentane (%)

or ZrO2 = 18% have extremely low catalytic activities

in n-pentane isomerization (profiles d and e in Fig. 8A).
The conversions of n-pentane were lower than 2%, and
iso-pentane selectivities were lower than 50%. Similar low
conversion (6.9%) and iso-pentane selectivity (64%) were
seen on the catalyst with 9.1%WO3 but higher ZrO2 content of 45% (profile d in Fig. 8B). The catalytic activity
increases drastically with the increases in WO3 and ZrO2
loadings. However, an optimal catalytic activity was observed on the supported catalyst with WO3 /ZrO2 weight
ratio of 0.50 and ZrO2 /SBA-15 weight ratio of 1.0 (sample 20%WO3 /40%ZrO2 /SBA-15). Further increase in either
WO3 or ZrO2 loading caused some decrease in n-pentane
conversion. Since the over-loaded samples have lower surface areas than sample 20%WO3 /40%ZrO2 /SBA-15, the decrease in catalytic activity is probably due to the blocking
of the mesoporous pores of SBA-15 by too large amounts
of WZ. In contrast, other samples of lower oxide loading
than sample 20%WO3 /40%ZrO2 /SBA-15 have higher surface areas. The lower catalytic activities of these catalysts
imply that factors other than surface area should play the
key role. It is noticed that the catalysts in profiles b, c
and d of Fig. 8B have the same WO3 contents (9.1, 15,
and 24%, respectively) as those in profiles b, c and d of
Fig. 8A, but different ZrO2 loadings. In comparison of the
catalysts of the same WO3 loading, the catalytic activities
in Fig. 8B are all higher than those in Fig. 8A. The ZrO2
loadings in the catalysts in Fig. 8B are in a close range
of 3845%, while those in Fig. 8A vary from 8.6 to 49%.
Based on these results, we conclude that the SBA-15 supported WZ must meet the requirement of specific ZrO2 size
(ZrO2 /SBA-15 about 1) and WO3 /ZrO2 ratio around 0.5,

40

40
0

10

15

20

TOS (h)
Fig. 9. Activity profiles of 1%Pt/20%WO3 /40%ZrO2 /SBA-15 catalyst for
three repeated runs.

T. Li et al. / Applied Catalysis A: General 261 (2004) 211219

4. Conclusions
W/Zr mixed oxides supported on mesoporous silica were
successfully prepared. For the mesoporous silica, SBA-15
was found to retain the ordered porous structure better than
MCM-41 after loading with W/Zr mixed oxide. Tungstated
zirconia was mainly dispersed inside the mesoporous channels of SBA-15, and the surface area and pore volume decreased with the loading. Both Lewis and Brnsted acid
sites are present on these samples, and the acidity of Lewis
acid sites was stronger than that of the Brnsted ones. The
SBA-15 supported and unsupported WO3 /ZrO2 materials
promoted with Pt in hydrogen environment were highly efficient in catalyzing n-pentane isomerization with a very
high selectivity of iso-pentane. Because the catalytic activity does not directly correlate to the acid amount, it is
proposed that the Brnsted acidic sites generated by the
spilt-over H+ species should play an important role in catalyzing the isomerization reaction. The mesoporous silica
supports play an important role in stabilizing the WZ catalyst
since the supported catalysts decayed slower than the unsupported one. Moreover, the catalytic activity of the SBA-15
supported WZ could be completely recovered by regeneration. The tungstated zirconia needs to meet the requirements
of specific size and W/Zr ratio to become the catalytic active sites for n-pentane isomerization. The optimal activity
was observed on SBA-15 supported with 1%Pt/20%WO3 /
40%ZrO2 .

Acknowledgements
We are grateful for the financial supports from China
Petroleum Corporation and the National Science Council of
Taiwan.

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