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APCAT 2182
Abstract
INTRODUCTION
EXPERIMENTAL
Two types of supports were employed in the preparation of the catalysts used
in this study: commercially available titania (Degoussa P-25)) which was used
as-received and titania modified by higher-valence cation doping. The dopant
materials were TazOs and W03. They were chosen on the basis of their valence
which is higher than that of the parent cation ( Ti4+ ) and on the basis of their
101
ionic radius which is similar-to that of the parent cation. This is an important
requirement for effective doping to occur.
Doping of the TiOp carriers was achieved by high temperature diffusion of
the doping cation into the crystal lattice of the carrier, following a procedure
which has been described elsewhere [ 71. Briefly, TiOz was mixed with the
oxide of the doping cation and after complete homogenization was achieved it
was fired in air at 900 oC for 5 h. The fact that doping does indeed occur follow-
ing this procedure has been determined by measurements of the electrical con-
ductivity and activation energy of electron conduction of undoped and doped
samples [ 111. The electrical conductivity of higher-valence doped titania was
found to be significantly higher than that of the undoped TiOz while the acti-
vation energy of electron conduction was significantly lower. The dopant level
was varied up to 4 wt.-%, on an oxide basis, in the case of Taz05 doping, and
up to 6 wt.-%, on an oxide basis, in the case of WOs.
A number of metallic catalysts consisting of Pt, Rh, Ru and Pd were pre-
pared on doped and undoped TiOa carriers, following the procedure of incipient
wetness impregnation [ 11.Details of catalyst characterization procedures by
selective chemisorptive titration with hydrogen, of kinetic measurements and
product analysis were also described earlier [ 11.It will only be stated here that
the intrinsic specific activity of catalyst formulations under benzene, naph-
thalene and biphenyl hydrogenation conditions was determined in a three-
phase slurry autoclave reactor operated in the batch mode at a temperature of
573 K and a hydrogen pressure of 65 atm. Kinetic experiments were conducted
in operating regions where interface and intraparticle transport resistance did
not influence measurable kinetic parameters.
RESULTS
Fig. 1. Influence of dopant concentration in the TiOp matrix on the hydrogen adsorption capacity
of Rh, Ru, Pd and Pt catalysts. ( 0 1, Rhodium; ( 0 1, ruthenium; (m 1, palladium; ( 0 1, platinum.
TiOz carrier. In the cases of Pd, Rh and Ru, the doping cation is W6+ while in
the case of platinum the doping cation is Ta+. However, similar results have
also been obtained when platinum is dispersed on W6+-doped TiOz [8] or
rhodium on Ta5+-doped TiO, [ 131. The H/M ratio represents the number of
adsorbed hydrogen atoms at complete monolayer coverage of the metallic sur-
face over the total number of metal atoms in the catalyst. It is apparent that
the hydrogen adsorption capacity of metals supported on doped TiO, carriers
is significantly altered and the degree of alteration is a function of the concen-
tration of the dopant in the carrier as well as of the particular metal. Thus,
doping of the carrier with higher-valence cations results in a significant in-
crease in the H/M ratio of Rh, Ru and Pd catalysts. The largest enhancement
of hydrogen adsorption capacity is observed over rhodium which exhibits an
H/M ratio which is approximately ten times larger than that exhibited by the
corresponding undoped catalyst. Platinum behaves in the exact opposite man-
ner. Its hydrogen adsorption capacity decreases significantly when it is dis-
persed on higher-valence doped TiOz, in agreement with earlier observations
[ 81. It must also be stated that the degree of alteration of the hydrogen ad-
sorption capacity of metals supported on doped TiOz carriers is a function of
the dispersion of the metal, or the size of the metal crystallites, as determined
in an earlier study [ 8,9].
Alterations in the hydrogen chemisorption capacity of metals dispersed on
higher-valence doped catalysts could be due to changes in metal dispersion on
103
the one hand, or due to some type of interaction between the metal crystallites
and the carrier, on the other. The first interpretation was investigated by per-
forming transmission electron microscopy (TEM) analysis of selected sam-
ples of Pt and Rh catalysts and by measurements of the CO adsorption capac-
ity of the same catalysts. Representative results in the form of H/M and CO/
M ratios and mean metal crystallite sizes estimated from hydrogen adsorption
and TEM microphotographs are shown in Table 1 [ 8,131. It is apparent that
TEM analysis failed to detect significant alterations in the mean metal crys-
tallite size (or degree of dispersion) when the metals are dispersed on higher-
valence doped TiOP. Furthermore, the CO/M ratio obtained over the rhodium
catalysts does not follow the behavior of the H/M ratio of the same catalysts,
as shown in Table 1. Measurements of the CO/M ratio of rhodium catalysts
as a function of the dopant content of the carrier show that this parameter goes
through a maximum with increasing dopant content, in contrast to the H/M
ratio [ 131. These results clearly demonstrate that the enhanced or reduced
hydrogen adsorption capacity of metal crystallites dispersed on higher-valence
doped TiO, is not a result of structural alterations of the metal particles in-
duced by doping of the carrier. It is probably due to an interaction at the metal-
support interface which alters the surface properties of the metal particles and
subsequently their adsorption capacity.
The abnormal adsorption of hydrogen on metal crystallites supported on
doped carriers introduces a complication in the estimation of the specific ac-
tivities (turnover frequencies or reaction rate constants) of these catalysts.
This is due to the fact that the metal dispersion or the number of exposed
surface metal atoms is usually estimated from hydrogen adsorption isotherms.
In the estimation of specific catalytic activity in this study, it was assumed that
the dispersion of the metals did not change upon doping of the carrier. Thus,
the dispersion obtained for the undoped catalysts was also used for the corre-
TABLE 1
Comparison of Hz and CO adsorption capacity and mean metal crystallite size as obtained by H2
chemisorption and TEM of Pt and Rh catalysts
H2 TEM
These values are erroneus since they do not account for the abnormal Hz adsorption capacity of
the catalysts dispersed on doped TiOz carriers.
104
0 50 loo 250
Time. min
Fig. 2. Test of the pseudo fiit order kinetic rate model with data obtained over various catalysts
under benzene and naphthalene hydrogenation. ( A ), Rh/TiOz (naphthalene); ( q ) Ru/TiOz (6
wt.-%) (benzene); (0) Pt/TiOz (benzene); (a), Rh/TiOz (4wt-% WOB) (naphthalene).
105
activity of Pt, Rh, Ru and Pd catalysts is shown in Figs. 3 and 4 for benzene
and naphthalene hydrogenation, respectively. Qualitatively similar results were
also obtained for biphenyl hydrogenation. The effects of higher-valence (w6+ )
carrier doping on hydrogenation activity are reflected in the ratio of the pseudo
first order reaction rate constants of the doped over the undoped catalysts,
/Q//Z. This ratio is shown in Figs. 3 and 4 as a function of the dopant (WO,)
concentration in the carrier. It is apparent that the specific hydrogenation
activity of Rh, Ru and Pd is enhanced when these metals are dispersed on
higher valence doped TiOa carriers. The degree of enhancement increases with
increasing dopant concentration in the carrier. Furthermore, the degree of en-
hancement of hydrogenation activity depends on the particular metal and on
the reactant. Thus, in all reaction systems, Rh seems to be the most sensitive
to carrier doping, followed by Ru and Pd. The enhancement of hydrogenation
activity of Rh under benzene hydrogenation is nearly one order of magnitude,
while, under naphthalene hydrogenation, it is approximately a factor of 40
higher. The enhancement of hydrogenation activity of Pd is about half that of
Rh. The directional influence of higher-valence carrier doping on the hydro-
genation activity of Pt is the opposite of that of the other metals. The specific
activity of Pt is drastically reduced when it is dispersed on doped carriers. In
fact, Pt loses approximately 90% of its hydrogenation activity upon higher-
valance doping of the carrier. The different behavior of Pt, as compared to that
of the other metals in both hydrogen adsorption capacity and hydrogenation
0 1 2 3 4 5 6
wt % dopant
Fig. 3. Variation of speciik activity of Rh, Ru, Pd and Pt for benzene hydrogenation wit dopant
concentration in the TiOp carrier. ( n ) , rhodium; ( 0 ) , ruthenium; ( 0 ) , palladium; ( 0 ) , platinum.
106
50
40
1
D \
20.
Oi
0 I2 3 L 5 b
wt% dopant
Fig. 4. Variation of specific activity of Rh, Ru, Pd and Pt for naphthalene hydrogenation with
dopant concentration in the TiOz carrier. Symbols as in Fig. 3.
activity has also been observed in other studies and in other reactions such as
CO hydrogenation and CO oxidation [9,12,13].
In naphthalene hydrogenation, product distribution might be an important
parameter, especially for coal liquefaction processes in which the liquid prod-
uct is recycled to the reactor to provide a source of transferable hydrogen. Thus,
an efficient catalyst should have sufficient hydrogenation activity for tetralin
formation. It should not, however, have excessive activity to over hydrogenate
and form poor hydrogen donors like decalin, according to the reaction scheme:
truns-Decalin
122
ki /
Naphthalene - Tetralin
\k3
cis-Decalin
In this reaction network kl, kz, and k3 are pseudo first order reaction rate con-
stants. Selectivity towards tetralin formation is defined by the ratio kl/h + k,.
The influence of altervalent carrier doping on selectivity towards tetralin for-
mation is reported in Table 2. It is apparent that the dispersion of Rh, Ru and
Pd on W6+-doped TiO, carriers results in the enhancement of selectivity to-
wards tetralin evolution. It is interesting to observe that selectivity enhance-
ment follows the order of activity enhancement of the specific metals. Thus,
107
TABLE 2
Catalyst Selectivity
(wk2+M
Pt/TiO, 15.1
Pt/TiOz (1 wt.-% Ta,05) 1.4
Rh/TiOz 3.2
Rh/TiOa (4 wt.-%_WO,) 8.8
Ru/TiO, 3.7
Ru/TiOz (4 wt.-% WOB) 17.7
Pd/TiOz 17
Pd/TiO, (4 wt.-% WO,) 22.5
20.
Fig. 5. Relative influence of higher-valence doping on rate constants for naphthalene to tetralin
and tetralin to decalins reaction routes. ( El ) , k* = k,; ( n ) , k* = b + k+ (a) rhodium; (b ) ruthenium.
the largest enhancement of selectivity with carrier doping is observed over Rh,
followed by Ru and Pd. Furthermore, the opposite trend is observed in the case
of Pt whose selectivity is drastically reduced when it is dispersed on higher-
valence doped TiOz. The hydrogenation activity of Pt was also reduced upon
doping of the carrier with higher valence cations.
It is interesting to observe the relative influence of carrier doping on the
108
0 l&J m 300
time,min
Fig. 6. Test of the pseudo first order kinetic rate model in the presence of 50 ppm of thiophene in
the reaction mixture. (0), Pd/TiOs (4 wt.-% WO,); (0) Rh/TiOs (4 wt.-% WOs); (0), Ru/
TiOp (4 wt.-% WO,); (m), Pt/TiOp.
TABLE 3
Influence of higher-valence carrier doping on sulfur tolerance of Pt, Rh, Ru and Pd catalysts
Catalyst kJk
Pt/TiOx 0.11
Pt/TiOx (1 wt.-% Ta,O,) 0.21
Rh/TiOx 0.20
Rh/TiOa (4 wt.-% WOx) 0.60
Ru/TiO* 0.27
Ru/TiOx (4 wt.-% WOx) 0.29
Pd/TiOz 0.29
Pd/TiOx (4 wt.-% WO,) 0.38
ratio k,/k of the doped catalysts is higher than that of the undoped ones. The
relative sulfur tolerance of the various metals is also revealed in Table 3. It is
apparent that Pd and Ru exhibit the highest tolerance to sulfur while Pt ex-
hibits the lowest tolerance. In all cases, however, sulfur tolerance is improved
when the metals are dispersed on higher-valence doped carriers. The largest
improvement is observed over Rh.
In comparing the sulfur tolerance of doped and undoped catalysts it must be
kept in mind that the doped catalysts are significantly more active than the
undoped ones. Thus, the beneficial influence of higher-valence carrier doping
on sulfur tolerance appears smaller than it actually is by the fact that the re-
110
-06
Fig. 7. Influence of the dopaut ( W03) concentration in the TiOp matrix on sulfur tolerance of Rh
under naphthalene hydrogenation in the presence of thiophene.
action rate constant of the doped catalysts is higher and tends to reduce the
ratio k.Jk.
The influenceof dopant ( W03) concentrationon sulfurtolerancewas more
formallyinvestigatedundernaphthalenehydrogenationconditionswith 50 ppm
thiophene in the reaction mixture.The influence of dopant concentration in
the carrieron the sulfurtolerance characteristicsof rhodiumcatalystsis illus-
trated in Fig. 7 in which the ratio kJk is shown as a function of dopant con-
centration.It is apparentthat this ratio, which representsthe resistanceof the
catalysts towards sulfur poisoning, increaseswith dopant concentration and
goes througha maximumat a dopant content of approximately4 wt.-%. Thus
the sulfur tolerance of rhodium is enhanced when it is dispersed on higher-
valence doped TiOz and it retains a maximum of 60% of its hydrogenation
activity in the presence of thiophene in the reaction mixture. The fact that
higher-valencecarrierdoping is beneficial to both, hydrogenationactivityand
sulfur tolerance, is also illustrated in Fig. 7 in the form of the ratio of the
reaction rate constants of the doped catalysts in the presence of sulfur, k+,
over the reaction rate constant of the undoped catalyst in the presence of sul-
fur, k,. The ratio b, s/lz, goes through a maximum at approximately4 wt.-%
WO, in the carrier.At this level of doping, in the presence of thiophene in the
reaction mixture,the doped catalystexhibits a toluene hydrogenationactivity
which is over two ordersof magnitudehigherthan that of the undopedcatalyst.
DISCUSSION
Semiconductor
t)
(a) (b)
Fig. 8. Electron energy band diagram of a metal and an n-type semiconductor with Qm > aa.. (a)
Neutral materials separated from each other. (b ) Thermal equilibrium situation after contact has
been made.
112
does not depend on doping is the electron affinity, x., defined as the energy
difference of an electron between the vacuum level and the lower edge of the
conduction band.
When a metal of work function @&,is brought into contact with an n-type
semiconductor of work function QS, and if the work functions are such that
CD,> @,, charge is transferred from the semiconductor into the metal until
their Fermi levels align. The electrons which cross-over into the metal leave a
positive charge of ionized donors behind, so that, a certain region in the semi-
conductor at the interface gets depleted of mobile electrons, as illustrated in
Fig. 8. The transferred electrons form a thin layer of negative charge contained
within the Thomas-Fermi screening distance from the interface. This process
causes band bending which is equal to the difference between the two work
functions. The amount of band bending is given by: QVi= t&,,- @, where q is
the charge and Vi is the contact potential barrier which an electron moving
from the semiconductor into the metal has to surmount.
The incorporation of higher valence cations into the TiOa matrix results in
an increased concentration of conduction electrons and a lowering of the work
function or upward shift of the Fermi energy level. This is illustrated by the
following defect reaction. WO,~W)Ti~2++Ti02+1/202(g)+2e- where
WITi12+ implies W in the lattice point of Ti producing positive charge, and e
is a conduction electron. Thus, the amount of charge transferred into the metal
crystallites is a function of the valence of the doping cation and of its concen-
tration in the Ti02 matrix.
As stated above, the electrons which are transferred into the metal particles
are concentrated in a thin layer near the interface and they are not distributed
into the particle. As a result, a dipole forms at the interface. Based on the
requirement that the Fermi level or electrochemical potential is uniform
throughout the crystal, if the crystal is sufficiently small (10-100 A) the work
function of the surface metal atoms is altered significantly. It is well-known
that chemisorptive and catalytic parameters depend appreciably (exponen-
tially) on the work function of the surface atoms since they involved redistri-
bution or shifts of electron clouds. It is for this reason that catalytic parameters
of metal crystallites supported on altervalent doped semiconductive carriers
are significantly altered.
The enhanced sulfur-tolerance of higher-valence doped catalysts is in phe-
nomenological contradiction with the charge transfer model which implies
lowering of the work function of surface metal atoms. This is due to the fact
that sulfide formation is an electron donor process for the metal and, as such,
would be favored by a reduced work function. However, sulfide formation is
preceded by a series of steps which involve molecular adsorption and surface
decomposition of the sulfur-containing species, thiophene in the present case.
The reduced work function of the metal particles probably hinders these steps
113
which involve electron transfer towards the metal. This results in reduced sul-
fide formation and stronger metal-sulfur bonds.
The directional influence of higher-valence carrier doping on the hydrogen
adsorption capacity and specific hydrogenation activity of Pt is opposite to
that of the other metals, namely Rh, Ru and Pd. This has also been observed
with other reaction systems [8,10,12,13]. The reasons for the different behav-
ior of Pt are the subject of current research activities.
ACKNOWLEDGEMENT
This work was funded in part by the Commission of the European Com-
munities, Non-Nuclear Energy R&D Programme under Contract No. EN3V-
0049-GR(TT).
REFERENCES