Applied Catalysis A: General 250 (2003) 65–73

Kinetic study of hydrogen adsorption on

Pt/WO3-ZrO2 and WO3-ZrO2
Sugeng Triwahyono, Takashi Yamada, Hideshi Hattori∗
Center for Advanced Research of Energy Technology, Hokkaido University, Sapporo 060-8628, Japan
Received 16 January 2003; received in revised form 14 March 2003; accepted 14 March 2003

Abstract
Rates of hydrogen adsorption on Pt/WO3 -ZrO2 and WO3 -ZrO2 were measured in the adsorption temperature range
323–573 K and the hydrogen pressure range 20–70 Torr (1 Torr = 133 Pa) to elucidate the rate-controlling step involved
in the hydrogen adsorption, the corresponding energy barrier, and the heat of adsorption. The hydrogen adsorption was faster
on Pt/WO3 -ZrO2 than on WO3 -ZrO2 . On both Pt/WO3 -ZrO2 and WO3 -ZrO2 , the adsorption continued for a long time. The
adsorption continued for more than 10 h for Pt/WO3 -ZrO2 below 373 K and for WO3 -ZrO2 below 473 K. The adsorption of
hydrogen involved the surface diffusion of hydrogen atoms for both adsorbents. For WO3 -ZrO2 , each hydrogen molecule
was dissociated on a specific site of WO3 -ZrO2 to form hydrogen atoms, which undergo surface diffusion over the surface
of WO3 -ZrO2 . The rate-controlling step was the surface diffusion of hydrogen atoms. The activation energy was 25.9 kJ/mol
for the surface diffusion. For Pt/WO3 -ZrO2 , two routes were operating. One route was same as that for WO3 -ZrO2 , and
the other route involved dissociation of hydrogen molecules on the Pt sites to form hydrogen atoms that undergo spillover
onto the WO3 -ZrO2 surface, followed by surface diffusion. For the latter route, the rate-controlling step was the spillover
step; its activation energy was 35.5 kJ/mol. The isosteric heats of adsorption of hydrogen on Pt/WO3 -ZrO2 were obtained as
11.6–8.0 kJ/mol for the hydrogen uptake range 2–3 × 1019 atom H/g cat. Similarities and differences in hydrogen adsorption
between SO4 2− -ZrO2 and WO3 -ZrO2 types are discussed.
© 2003 Elsevier Science B.V. All rights reserved.
Keywords: Pt/WO3 -ZrO2 ; WO3 -ZrO2 ; Hydrogen adsorption; Spillover; Surface diffusion

1. Introduction WO3 -ZrO2 are similar to those of SO4 2− -ZrO2 , which

Tungsten oxide promoted zirconia (WO3 -ZrO2 )
possesses acid sites and acts as an efficient catalyst for
isomerization, cracking, and alkylation of hydrocar-
bons [1–5]. The catalytic activities of WO3 -ZrO2 for
the skeletal isomerization of alkanes are improved by
addition of Pt to the catalyst and by carrying out the
reaction in the presence of hydrogen. These features of
∗ Corresponding author. Tel.: +81-11-706-7119;
fax: +81-11-726-0731.
E-mail address: hattori@carbon.caret.hokudai.ac.jp (H. Hattori).
also possesses strong acid sites and exhibits high ac-
tivity for the isomerization of alkanes [6–8]. We pro-
posed a concept of “Molecular-hydrogen-originated
protonic acid sites” that involves generation of pro-
tonic acid sites on the surface of Pt/SO4 2− -ZrO2
[9,10]. Hydrogen molecules are adsorbed on Pt sites
to form hydrogen atoms that spill over onto the
support SO4 2− -ZrO2 and undergo surface diffusion.
Each spiltover hydrogen atom reaches a Lewis acid
site and donates an electron to form an H+ . The H+
is stabilized on an O atom near the Lewis acid site.
The Lewis acid site trapping an electron reacts with a

0926-860X/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0926-860X(03)00302-8
66 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73

second spiltover hydrogen to form an H− bound to a 2.2. Hydrogen adsorption

Lewis acid site.
We also reported the results of hydrogen adsorp- The hydrogen uptake was measured by the au-
tion on Pt/SO4 2− -ZrO2 and SO4 2− -ZrO2 [11]. The tomatic gas adsorption apparatus Belsorp 28SA. A
hydrogen adsorption on Pt/SO4 2− -ZrO2 continued for catalyst sample was placed in an adsorption vessel
a long time; equilibrium could not be reached even and pretreated in hydrogen flow at 673 K for 2 h, fol-
after 24 h at an adsorption temperature of 523 K, and lowed by outgassing at 673 K for 2 h, and then cooled
hydrogen uptake exceeded H/Pt ratio of unity. By ki- to an adsorption temperature and held at that temper-
netic analysis of the adsorption, it was concluded that ature for 3 h. The adsorption temperature was varied
the rate-controlling step in the adsorption was the sur- from 323 to 573 K. Hydrogen was introduced into
face diffusion of the spiltover hydrogen atoms over the adsorption system, and the pressure change was
the surface of SO4 2− -ZrO2 . The surface diffusion of monitored with time. The initial pressure of hydrogen
hydrogen atoms became appreciable above 473 K for was varied from 20 and 70 Torr (1 Torr = 133 Pa)
Pt/SO4 2− -ZrO2 . in the monitoring of the effect of initial pressure for
Recently, we reported on the basis of IR studies Pt/WO3 -ZrO2 . The hydrogen uptake was calculated
of adsorbed pyridine that the concept “Molecular- from the pressure change.
hydrogen-originated protonic acid sites” is also ap-
plicable to Pt/WO3 -ZrO2 and WO3 -ZrO2 [12]. The
3. Results
generation of protonic acid sites from hydrogen
molecules was appreciable even at room temperature 3.1. Hydrogen uptake on Pt/WO3 -ZrO2
for Pt/WO3 -ZrO2 and at 373 K for WO3 -ZrO2 . Results
thus suggested that the formation of an H+ is much Fig. 1 shows the variations of hydrogen uptake
easier for Pt/WO3 -ZrO2 than for Pt/SO4 2− -ZrO2 , and on Pt/WO3 -ZrO2 as a function of time at different
that hydrogen can be adsorbed to a considerable ex-
tent on WO3 -ZrO2 free of Pt, in contrast to almost
no adsorption on SO4 2− -ZrO2 . In the present study,
the rates of hydrogen adsorption on Pt/WO3 -ZrO2
and WO3 -ZrO2 were measured to elucidate the
rate-controlling step involved in the hydrogen adsorp-
tion, the corresponding energy barrier, and the heat of
adsorption. We try to clarify the similarity and differ-
ence between SO4 2− -ZrO2 -type and WO3 -ZrO2 -type
catalysts.

2. Experimental

2.1. Catalyst preparation

The WO3 -ZrO2 sample was prepared by impreg-

nation of Zr(OH)4 with aqueous (NH4 )6 [H2 W12 O40 ],
followed by calcination at 1093 K in air. The sur-
face area was 51 m2 /g and the content of WO3 was
13 wt.%.
The Pt/WO3 -ZrO2 sample was prepared by impreg-
Fig. 1. Variations of hydrogen uptake on Pt/WO3 -ZrO2 as a func-
nation of the WO3 -ZrO2 with aqueous H2 PtCl6 fol-
tion of time at different temperatures. (a) 323 K; (b) 373 K; (c)
lowed by calcination at 723 K in air. The surface area 423 K; (d) 473 K; (e) 523 K; and (f) 573 K. Initial hydrogen pres-
was 53 m2 /g and the content of Pt was 0.5 wt.%. sure was 50 Torr.
 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73 67

Fig. 2. Variations of hydrogen uptake on Pt/WO3 -ZrO2 at 498 K Fig. 3. Plot of equilibrium hydrogen uptake vs. pressure for hy-
as a function of time at different hydrogen pressures. (a) 25 Torr; drogen adsorption on Pt/WO3 -ZrO2 at (a) 473 K; (b) 498 K; and
(b) 40 Torr; and (c) 60 Torr. (c) 523 K.

temperatures. The initial hydrogen pressures were 3.2. Hydrogen adsorption on WO3 -ZrO2
50 Torr (6.7 kPa). For the initial few minutes, very
fast adsorption occurred at all the temperatures. A
Fig. 4 shows the variations of hydrogen uptake on
slow hydrogen adsorption followed the fast adsorp-
WO3 -ZrO2 as a function of time at different temper-
tion. Above 373 K, hydrogen adsorption reached
atures. The initial hydrogen pressures were 50 Torr.
equilibrium within 6 h. At equilibrated state, the hy-
Unlike the adsorption on Pt/WO3 -ZrO2 , the adsorp-
drogen uptake was larger for the adsorption at lower
tion on Pt-free WO3 -ZrO2 was not so fast in the initial
temperature, which is expected because the process
stage of adsorption. Over the adsorption temperature
for general adsorption is exothermic. Below 373 K,
range 323–473 K, hydrogen uptake increased slowly
hydrogen adsorption did not reach equilibrium even
with time, and did not reach equilibrium even after
after 10 h. Hydrogen uptake was still increasing over
10 h. Hydrogen uptakes in 10 h increased with an in-
10 h at an adsorption temperature of 323 K.
crease for the adsorption temperature up to 473 K.
Fig. 2 shows the variations of hydrogen uptake on
Above 523 K, however, hydrogen adsorption reached
Pt/WO3 -ZrO2 as a function of time at different initial
equilibrium in less than 6 h.
pressures of hydrogen at a constant temperature of
498 K. The hydrogen pressure decreased as adsorp-
tion proceeded, but the pressure decrease was at most 4. Discussion
15.7 Torr. At 498 K, adsorption of hydrogen reached
equilibrium in 10 h. Similar figures were obtained
Characteristic features of hydrogen adsorption on
when hydrogen uptakes were measured as a function
Pt/WO3 -ZrO2 and WO3 -ZrO2 are summarized as
of time at 473 and 523 K, though these are not shown.
follows.
From the hydrogen uptakes at equilibrium at different
temperatures and pressures, adsorption isotherms at 1. Hydrogen adsorption on Pt/WO3 -ZrO2 continued
473, 498, and 523 K are shown in Fig. 3. for more than 10 h at the adsorption temperature
68 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73
Fig. 4. Variations of hydrogen uptake on WO3 -ZrO2 as a function
of time at different temperatures. (a) 323 K; (b) 373 K; (c) 423 K;
(d) 473 K; (e) 523 K; and (f) 573 K. Initial hydrogen pressure was
50 Torr.
below 373 K, while it reached equilibrium within
10 h at and above 373 K.
2. Hydrogen uptake on Pt/WO3 -ZrO2 exceeded the
H/Pt ratio of unity.
3. Hydrogen adsorption was faster for Pt/WO3 -ZrO2
than for WO3 -ZrO2 .
4. Hydrogen uptake on WO3 -ZrO2 increased for at
least 6 h with an increase in the adsorption temper-
ature in the temperature range 323–473 K, while it
reaches equilibrium within 6 h at and above 523 K.
We have reported a kinetic study of hydrogen ad-
sorption on Pt/SO4 2− -ZrO2 and SO4 2− -ZrO2 [11].
The hydrogen adsorption on Pt/SO4 2− -ZrO2 was char-
acterized by the spillover of hydrogen atoms, followed
by surface diffusion. General trends of hydrogen ad-
sorption were similar for SO4 2− -ZrO2 and WO3 -ZrO2
types. For both types of catalysts, hydrogen adsorption
continued for a long time, and, in a certain range of
adsorption temperature, hydrogen uptake was larger as
the adsorption temperature became higher. The hydro-
gen adsorption should involve a step that has an energy
barrier to be crossed for both types of catalysts. Also,
the H/Pt ratio exceeds unity for both Pt/SO4 2− -ZrO2
and Pt/WO3 -ZrO2 .
There are also differences between SO4 2− -ZrO2
and WO3 -ZrO2 types. While hydrogen uptake was
negligibly small for SO4 2− -ZrO2 without Pt, hydro-
gen uptake was considerable for WO3 -ZrO2 . It seems
that WO3 -ZrO2 possesses the sites to dissociate hy-
drogen molecules while SO4 2− -ZrO2 does not possess
such sites.
The other difference between SO4 2− -ZrO2 and
WO3 -ZrO2 types was observed in the rate of hydro-
gen adsorption. For Pt/SO4 2− -ZrO2 , adsorption equi-
librium was not established in 24 h at an adsorption
temperature of 523 K. For Pt/WO3 -ZrO2 , however,
the equilibrium was established in 6 h at temper-
atures above 423 K. Even for Pt-free WO3 -ZrO2 ,
the equilibrium was established within 6 h at
523 K.
Because the hydrogen uptake on Pt-free WO3 -ZrO2
is considerable, the hydrogen adsorption on Pt/WO3 -
ZrO2 should occur through two different routes: one
involving adsorption on Pt sites, and the other oc-
curring directly on WO3 -ZrO2 and not involving
adsorption on Pt sites. The hydrogen uptake through
adsorption on Pt sites may be expressed by subtraction
of the hydrogen uptake on WO3 -ZrO2 from the total
hydrogen uptake on Pt/WO3 -ZrO2 . The subtracted
hydrogen uptakes on Pt/WO3 -ZrO2 as a function of
time at different adsorption temperatures are shown
in Fig. 5. At 323 and 373 K, the hydrogen uptakes
increased with time and reached equilibrium in 6 h.
However, at and above 423 K, the hydrogen uptakes
increased in the initial period of adsorption and then
began to decrease. The period of time needed to give
maxima of the hydrogen uptake became shorter with
an increase in the adsorption temperature.
Hydrogen uptake should smoothly increase with
time, through whatever route the hydrogen adsorption
occurs. Appearance of maxima of the hydrogen up-
take calculated by the subtraction of the hydrogen up-
take on WO3 -ZrO2 from the total hydrogen uptake
indicates that the hydrogen adsorption directly occur-
ring on the WO3 -ZrO2 surface of Pt/WO3 -ZrO2 and
the hydrogen adsorption occurring through Pt interfere
with each other. The hydrogen adsorption occurring
directly on the WO3 -ZrO2 surface of Pt/WO3 -ZrO2
should be suppressed by the hydrogen adsorption oc-
curring through Pt, and vice versa.
 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73
Fig. 5. Variations of hydrogen uptake on Pt/WO3 -ZrO2 through
Pt sites as a function of time at different temperatures. (a) 323 K;
(b) 373 K; (c) 423 K; (d) 473 K; (e) 523 K; and (f) 573 K.
The subtracted hydrogen uptake increased smoothly
with time when adsorption was performed at 323 and
373 K. This is because the hydrogen uptake through
direct adsorption on WO3 -ZrO2 was small, and the hy-
drogen adsorption through Pt was not influenced much
by the hydrogen adsorption through direct adsorption.
These hydrogen uptakes calculated by the subtraction
may be subjected to kinetic analysis for the adsorption
route through Pt.
In Fig. 5, one can also observe that the subtracted
hydrogen uptake reached constant values for curves
(e) and (f), for which adsorption temperatures were
523 and 573 K, respectively. The constant values of
the hydrogen uptake indicate the hydrogen uptake on
Pt sites.
The adsorption of hydrogen on Pt/WO3 -ZrO2
through Pt sites is suggested to involve the successive
three steps: hydrogen dissociation on Pt sites, spillover
of the dissociated hydrogen onto the WO3 -ZrO2 sur-
face, and surface diffusion of the spiltover hydrogen.
The word “spillover” is used with different meanings
depending on the literature. In some cases, “spillover”
includes the surface diffusion that follows the trans-
69
portation of a certain species from one phase to the
other. In the present paper, “spillover” means only the
transportation of a certain species from one phase to
the other, and does not include the surface diffusion.
For hydrogen adsorption on WO3 -ZrO2 , it is not
certain as to whether the sites to adsorb hydrogen
molecule to dissociate are different from or same
as those on which spiltover hydrogen atoms diffuse
and/or hydrogen atoms are finally fixed in the forms
of H+ and H− . Whatever the sites to adsorb hydro-
gen molecules to dissociate to form hydrogen atoms
are, the adsorption of hydrogen on WO3 -ZrO2 is
suggested to involve at least two successive steps:
hydrogen dissociation to form hydrogen atoms, and
surface diffusion of the hydrogen atoms. If the sites
to dissociate hydrogen molecules are different from
those over which hydrogen atoms diffuse, the step of
transportation of hydrogen atoms from the former to
the latter sites should be taken into account in between
the two successive steps: dissociation of hydrogen
molecule and surface diffusion. Even if a step of such
transportation is involved, the step of dissociation of
hydrogen molecule and the step of the transformation
can be combined and expressed as the step to form
hydrogen atoms.
In the case where the formation of hydrogen atoms
is the rate-controlling step, the rate of hydrogen ad-
sorption on WO3 -ZrO2 would be expressed by
dC
= k(Ce − C) (1)
dt
where C represents the concentration of the spiltover
hydrogen on the WO3 -ZrO2 , and Ce represents the
concentration of the spiltover hydrogen on the WO3 -
ZrO2 equilibrated with the hydrogen in gas phase. The
value of C should be the same for the whole surface
of WO3 -ZrO2 .
Integration of Eq. (1) yields


C
−ln 1 − = kt (2)
Ce
Eq. (2) can be expressed by


M
−ln 1 − = kt (3)
Me
where M and Me represent the hydrogen uptakes at t
and equilibrium, respectively.
70 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73

tance from the center of hydrogen dissociation site,

and the diffusion coefficient of the hydrogen atom, re-
spectively.
The initial and boundary conditions are C = 0 when
t = 0 and x > a, and C = C0 at x = a when t > 0,
where a and C0 represent the radius of the hydrogen
dissociation site, and the concentration of the hydro-
gen atom on the diffusing surface equilibrated with the
hydrogen on the hydrogen dissociation site, respec-
tively. These conditions are based on the diffusion into
a semi-infinite surface.
Introduction of suitable boundary conditions into
Eq. (4) yields the following equations when Dt/a2 is
small [11]:
M = 4π1/2 aC0 D1/2 t 1/2 (5)

where M represents the hydrogen uptake, that is, the

Fig. 6. Plot of −ln(1 − M/Me ) vs. t for hydrogen adsorption on
WO3 -ZrO2 at different temperatures. (a) 323 K; (b) 373 K; (c)
423 K; (d) 473 K; (e) 523 K; and (f) 573 K.
amount of the diffusing hydrogen atoms.
Plots of M versus t1/2 for different adsorption tem-
peratures are shown in Fig. 7; all plots showed straight
lines. However, the straight lines do not cross the ori-
gin. The time scale on which the lines cross the ab-
scissa axis is at most 250 s. In the very beginning of

The plots of −ln(1 − M/Me ) versus t are shown

in Fig. 6. Since the values of Me are unknown for
adsorption temperatures below 473 K, we applied the
value of M at 473 K and in 10 h for the values of
Me of the adsorption temperatures below 473 K. The
real values of Me of the adsorption temperatures be-
low 473 K should be larger than the value applied.
Straight lines were obtained only for the adsorptions
at 523 and 573 K. However, the plots for the adsorp-
tion below 473 K deviated much from the straight line.
These results suggest that at and below 473 K the for-
mation of hydrogen atoms is not the rate-controlling
step. Above 473 K, the straight lines may suggest that
the rate-controlling step is the formation of hydrogen
atoms from hydrogen molecules.
In the case where the surface diffusion is the
rate-controlling step, the rate of adsorption would be
expressed by the equation for Fick’s second law for
surface diffusion:



∂C D ∂ ∂C
= x (4)
∂t x ∂x ∂x
Fig. 7. Plot of hydrogen uptake vs. t1/2 for hydrogen adsorption
where C, x, and D represent the surface concentration on WO3 -ZrO2 at different temperatures. (a) 323 K; (b) 373 K; (c)
of hydrogen atom diffusing over the surface, the dis- 423 K; (d) 473 K; (e) 523 K; and (f) 573 K.
 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73 71

face diffusion, and the other involving direct adsorp-

tion on WO3 -ZrO2 surface without participation of Pt
sites.
In general, hydrogen adsorption on Pt sites is
fast; the adsorption occurs readily at room tempera-
ture. Therefore, hydrogen adsorption on the Pt sites
in Pt/WO3 -ZrO2 should not be the rate-controlling
step.
In the case where the spillover step is the
rate-controlling step, the rate of adsorption would be
expressed by Eq. (1). Integration of Eq. (1) yields
Eq. (2), but we have to take into account the hydro-
gen uptake on Pt species. C/Ce is not equal to M/Me
because M and Me include the hydrogen uptake on
Pt species. Eq. (2) can be reformed as follows by
substitution of C = M − A and Ce = Me − A, where
A represents the hydrogen uptake on Pt sites.


C
−ln 1 − = −ln(Me − M) + ln(Me − A) (6)
Ce
Fig. 8. Arrhenius plot for hydrogen adsorption on WO3 -ZrO2 . Fig. 9 plots −ln(Me − M) versus t for the hydro-
gen adsorption on Pt/WO3 -ZrO2 through Pt sites at
323, 373, and 423 K (data of curves (a), (b), and (c)
adsorption, the adsorption would not proceed in steady
state; the temperature and pressure may fluctuate. The
deviation of the lines from the origin may arise from
the unsteady state of the initial period of adsorption.
The slope of the plot M versus t1/2 is proportional to
the square root of the diffusion constant D. Activation
energy for the diffusion is obtained by an Arrhenius
plot of the square of the slope. The Arrhenius plot is
shown in Fig. 8. The activation energy is obtained as
25.9 kJ/mol.
As shown in Fig. 7, the plots of M versus t1/2 give
straight lines when adsorption was performed at and
above 473 K. The plots of −ln(1−M/Me ) versus t also
give straight lines for the adsorption above 473 K. It is
not certain which step is the rate-controlling step at and
above 473 K. It is possible that the slow step changes
with adsorption temperature, and that the temperature
range 473–523 K is the transition temperature range
over which the rate-controlling step changes from the
surface diffusion of hydrogen atoms to the formation
of hydrogen atoms.
For the adsorption of hydrogen on Pt/WO3 -ZrO2 ,
hydrogen adsorption may occur by two independent Fig. 9. Plot of −ln(Me − M) vs. t for hydrogen adsorption on
routes as described earlier: one involving hydrogen Pt/WO3 -ZrO2 through Pt sites at different temperatures. (a) 323 K;
adsorption on Pt sites followed by spillover and sur- (b) 373 K; and (c) 423 K.
72 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73

84 kJ/mol [11]. In the present study, it was shown

Fig. 10. Plot of hydrogen uptake vs. t1/2 for hydrogen adsorption
on Pt/WO3 -ZrO2 through Pt sites at different temperatures. (a)
323 K and (b) 373 K.
that the activation energy of the surface diffusion of
hydrogen atoms on WO3 -ZrO2 is 25.9 kJ/mol, and
the rate-controlling step for the hydrogen adsorption
on Pt/WO3 -ZrO2 is the spillover of hydrogen atoms
on Pt sites onto the WO3 -ZrO2 surface. We have also
reported that protonic acid sites are generated by ad-
sorption of hydrogen both on Pt/SO4 2− -ZrO2 [10] and
Pt/ WO3 -ZrO2 [12]. However, temperature required
for the generation of protonic acid sites was higher
for Pt/SO4 2− -ZrO2 than for Pt/WO3 -ZrO2 . The dif-
ference in the temperature required is suggested to
be caused by the easiness of the surface diffusion of
hydrogen atoms.
Finally, isosteric heats of adsorption of hydrogen
are calculated by applying the Clapeyron–Clausius
equation to the adsorption isotherms at different tem-
peratures as shown in Fig. 3. Fig. 11 shows isos-
teric heat of adsorption as a function of hydrogen up-
take. The isosteric heats of adsorption are obtained as
11.6–8.0 kJ/mol for the hydrogen uptake range 2–3 ×
1019 atom H/g cat.

in Fig. 5). The plots in Fig. 9 give straight lines. From

the slopes, we can obtain rate constants k’s at differ-
ent temperatures. The activation energy is obtained as
35.5 kJ/mol by Arrhenius plot for the k’s. Thus, the
slow step for the hydrogen adsorption through Pt sites
on Pt/WO3 -ZrO2 is the step of spillover of hydrogen
atoms on the Pt site onto the WO3 -ZrO2 surface.
Plots of M versus t1/2 for the hydrogen adsorption
on Pt/WO3 -ZrO2 at 323 and 373 K through Pt sites,
which correspond to curves (a) and (b) in Fig. 5, are
shown in Fig. 10. Neither curve (a) nor (b) gives a
straight line. It is obvious that the surface diffusion
step is not the rate-controlling step for the hydrogen
adsorption on Pt/WO3 -ZrO2 through Pt sites.
For the adsorption of hydrogen on Pt/WO3 -ZrO2
through Pt sites above 423 K, it was impossible to de-
termine which step is the rate-controlling step because
the adsorption through Pt sites could not be separated
from the adsorption directly occurring on WO3 -ZrO2 .
We have reported in a previous paper on the ad-
sorption of hydrogen on Pt/SO4 2− -ZrO2 that the
rate-controlling step is surface diffusion of hydrogen Fig. 11. Plot of heat adsorption of hydrogen vs. hydrogen uptake
atoms, and the activation energy of the diffusion is for hydrogen adsorption on Pt/WO3 -ZrO2 .
 S. Triwahyono et al. / Applied Catalysis A: General 250 (2003) 65–73
5. Summary
1. Hydrogen adsorption on Pt/WO3 -ZrO2 is faster
than that on WO3 -ZrO2 .
2. Hydrogen adsorption on both Pt/WO3 -ZrO2 and
WO3 -ZrO2 involves dissociation of hydrogen
molecules to hydrogen atoms and surface diffusion
of hydrogen atoms. For Pt/WO3 -ZrO2 , spillover
of hydrogen atoms on Pt sites onto WO3 -ZrO2 is
involved.
3. The rate-controlling steps are the spillover step
for Pt/WO3 -ZrO2 and the surface diffusion step
for WO3 -ZrO2 ; activation energies are 35.5 and
25.9 kJ/mol for the spillover step and the surface
diffusion step, respectively.
4. Isosteric heats of adsorption on Pt/WO3 -ZrO2 are
11.6–8.0 kJ/mol for the hydrogen uptake range
2–3 × 1019 atom H/g cat.
Acknowledgements
This work was supported by Grant-in aid for Sci-
entific Research, the Ministry of Education, Sports,
Culture, Science and Technology, Japan.
73
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