Applied Catalysis A: General, 80 (1992) 99-113 99

Elsevier Science Publishers B.V., Amsterdam

APCAT 2182

Hydrogenation of aromatic compounds over noble metals

dispersed on doped titania carriers

M. Koussathana, N. Vamvouka, M. Tsapatsis and X. Verykios*

Institute of Chemical Engineering and High Temperature Chemical Processes, Department of
Chemical Engineering, University of Patras, GR 26110 Patras (Greece), tel. (+30-61)991527,
fax. (+30-61)993255, e-mail VERYKZOS@GRPATVXl
(Received 16 July 1991)

Abstract

The slurry-phasehydrogenationof aromatic compounds such as benzene, naphthaleneand biphenyl

is used to investigatethe influence of altervalentcarrier doping on the apecifx hydrogenationactivity
of Pt, Rh, Ru and Pd catalysts.The metalsare dispersedon TiOz carriersdoped with cations of valence
higher than that of the parent cation, such as W+ and Ta5+. Doping is achieved by high temperature
diffusion of the doping cation into the crystal lattice of the carrier. It is shown that the hydrogen ad-
sorption capacity of Rh, Ru and Pd is enhanced upon doping of the carrier and the degreeof enhance-
ment is a function of dopant concentrationin the carrier.The samemetalsalso exhibit enhancedactivity
for benzene,naphthaleneand biphenyl hydrogenationand improved sulfurtolerancewhen thiophene is
used as the sulfursource. Platinum, however,exhibits reducedhydrogenuptakecapacity and hydrogen-
ation activity when it is dispersedon higher-valencedoped TiO, carriers.These observationsare inter-
preted in terms of an electronic interaction developingat the metal-support interface,as a result of the
doping process, which causesa loweringof the work function of surface metal atoms.

Keywords: aromatic compounds, doping, hydrogenation,noble metal catalysts,titania.

INTRODUCTION

The slurry-phase hydrogenation of aromatic compounds over A1203- and

TiO,-supported monometallic and bimetallic catalysts was discussed in a pre-
vious publication [ 11.The aromatic compounds employed in these studies were
selected to resemble those prevalent in heavy hydrocarbon feedstocks or in
coal-derived liquids. Hydrocarbon liquids derived from coal liquefaction pro-
cesses contain large quantities of highly unsaturated compounds and signifi-
cant quantities of heteroatoms. The production of clean-burning fuels from
these liquids requires removal of the heteroatoms and hydrogenation of the
unsaturated hydrocarbons to improve the hydrogen-to-carbon ratio. These goals
are achieved employing metal sulfide catalysts under severe operating
conditions.
In the present study the hydrogenation of aromatic compounds over metallic

0926-869X/92/$05.00 0 1992 Elsevier Science Publishers B.V. All rights reserved.

100

surfaces is investigated. Particular attention is paid to alterations of the geo-

metric and electronic structure of the metallic surfaces so as to enhance their
hydrogenation activity and, primarily, to improve their sulfur tolerance char-
acteristics. In a previous communication [ 1 ] the influence of a secondary metal
(Pd, Re, Ir) on the hydrogenation activity and sulfur tolerance of Group VIII
metals (Pt, Rh, Ru) was discussed. It was shown that, in most cases, bimetallic
formulations exhibit enhanced hydrogenation activity and improved sulfur
tolerance characteristics, as compared to their monometallic counterparts. This
was found to be particularly true in the cases of Rh-Re and Ru-Re bimetallic
formulations.
The influence of altervalent carrier doping on chemisorption characteristics,
hydrogenation activity and sulfur tolerance of monometallic catalyst formu-
lations is discussed in the present communication. Many investigations have
been inspired by the possibility that an interaction between metal crystallites
and support materials can alter the catalytic performance of the former. Strong
evidence for this concept has been provided by Sinfelt and his co-workers [ 2-
4] and later by other investigators who showed that kinetic parameters of cer-
tain reaction systems were influenced by the particular support employed to
disperse the metal. Early work by Schwab [5] and Solymosi [6] attempted to
explore and manipulate metal-support interactions which were induced by
doping of supports with altervalent cations. More systematic work in this field
has been conducted recently [7-131. Significant evidence has been accumu-
lated in these studies pointing towards an electronic interaction at the metal-
support interface which alters the work function of surface metal atoms and
thus their chemisorptive and catalytic properties. This interaction is induced
by the doping of semiconductive carriers with altervalent cations.
The influence of dopant-induced metal-support interactions on chemisorp-
tion capacity, hydrogenation activity and sulfur tolerance of metallic catalysts
is discussed in the present communication. The metals selected for this pur-
pose are Pt, Pd, Rh and Ru. They were dispersed on undoped and higher-
valence doped TiOz carriers and their hydrogen adsorption capacity as well as
their specific hydrogenation activity were determined as a function of dopant
concentration in the carrier. Their sulfur tolerance characteristics were deter-
mined by addition of thiophene in the reaction mixture.

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

Hydrogen uptake capacity of doped catalysts

The hydrogen uptake capacity of supported metal catalysts is an important

parameter since it is not only used to determine the degree of dispersion and
the mean metal crystallite size, but also the affinity of the surface towards
hydrogen, which might be a good indicator of the hydrogenation activity of the
surface. The hydrogen uptake capacity of catalysts prepared in the course of
this study was determined by selective chemisorption of hydrogen at 298 K
[ 11. Hydrogen adsorption isotherms of doped and undoped catalysts were found
to be well-behaved and saturation capacity was achieved at hydrogen pressures
between 100 and 150 Torr. Saturation capacities were obtained by extrapola-
tion of the linear portions of the isotherms to zero pressure, which is a standard
procedure.
The hydrogen uptake capacity of metallic catalysts is shown in Fig. 1 in the
form of hydrogen-to-metal ratio (H/M) as a function of dopant content of the
 wf% dopant

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

Catalyst H/M CO/M Mean crystallite diameter (A)

H2 TEM

Pt/TiOz 0.73 0.92 22

Pt/TiO, (1 wt.-% Taz05) 0.12 0.23 34
Rh/TiO, 0.10 0.10 110 82
Rh/TiO, (2 wt.-% WOB) 0.63 0.37 (19Y 64

These values are erroneus since they do not account for the abnormal Hz adsorption capacity of
the catalysts dispersed on doped TiOz carriers.
104

sponding doped ones. As stated earlier, this assumption is supported by results

of TRM analysis which show that the average size of the metal crystallites of
doped catalysts is not significantly different than that of the corresponding
undoped catalysts.

Influence of carrier doping on specific hydrogenation activity

The influence of altervalent carrier doping on the specific hydrogenation

activity of Pt, Rh, Ru and Pd catalysts was investigated in a three-phase slurry
reactor [ 11. Benzene, naphthalene and biphenyl were selected as model com-
pounds on the basis of their resemblance to the structure of aromatic compo-
nents found in heavy hydrocarbon feedstocks or in coal-derived liquids. Me-
tallic catalysts were prepared on higher-valence doped TiOp carriers with
variable dopant concentration. In all cases, reaction kinetics were found to be
pseudo first order with respect to the hydrocarbon and apparent zero order
with respect to hydrogen, which was in excess. Tests of the rate model, con-
ducted with data of representative experiments, are shown in Fig. 2. Specific
reaction rate constants are estimated from such plots and converted on a basis
of g mol of surface metal atoms, since the number of exposed surface metal
atoms per unit mass of catalyst is known from hydrogen adsorption experi-
ments as discussed in the previous section. Thus, activities reported in the
form of rate constants account for different dispersions of the catalysts. As
discussed earlier, however, the dispersion of doped catalysts was assumed to
be equal to that of corresponding undoped ones.
The influence of altervalent carrier doping on the specific hydrogenation

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

Influence of higher-valence carrier doping on selectivity towards tetralin formation

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

naphthalene to tetralin and tetralin to decalin hydrogenation reactions. This

is illustrated in Fig. 5 in which both ratios, /z&k1 and (& + $)d/ (& + &) are
shown, in the form of bar diagrams, as a function of the dopant content of the
carrier for results obtained over the Rh and Ru catalysts. It is apparent that
although all reaction rate constants increase upon higher-valence doping of
the carrier the naphthalene to tetralin rate constant increases more than the
tetralin to decalin rate constants. As a result, selectivity towards tetralin for-
mation is improved, as shown in Table 2.

Influence of carrier doping on sulfur tolerance

The sulfur poisoning resistance of catalysts intended to be used in hydro-

genation processes is a critical parameter since the metallic surfaces must re-
tain their hydrogenation activity in the presence of sulfur-containing com-
pounds which are found in heavy hydrocarbon feedstocks, especially in oils
originating from coal liquefaction processes. The poisoning characteristics of
the various catalyst formulations were obtained by addition of 50 to 200 ppm
of thiophene in the reaction mixture, exposure of the catalysts to this mixture
for approximately one hour prior to initiation of the reaction and determina-
tion of reaction rate constants for the hydrogenation reactions under these
conditions.
Kinetic rate constants were determined following the usual procedure, as-
suming pseudo first order kinetic rate expressions. The phenomenon of cata-
lyst poisoning, however, is a dynamic one and its true characteristics can only
be determined with a continuous flow reactor. In the methodology of the pres-
ent study, employing a batch reactor, it is assumed that the poison containing
compound adsorbs reactively on the metallic surface and equilibrium is estab-
lished between the sulfur-containing species and the surface prior to initiation
of the reaction. Thus, the catalytic surface is not significantly altered during
the course of the reaction. The validity of this assumption is supported by the
kinetic data obtained, some of which are shown in Fig. 6. The fact that the
linear relationships are retained over the entire course of the reaction indicates
that the catalyst surface is not significantly altered during the course of the
reaction.
The effects of higher valence cation doping of TiO, on the sulfur poisoning
resistance of certain metallic catalysts, as derived under naphthalene hydro-
genation experiments are shown in Table 3, in the form of the ratio of the rate
constant in presence (k,) and absence (k) of poison, k,/k. This ratio tends to
unity when the catalyst is completely resistant to sulfur or to zero when the
catalyst is poisoned very rapidly. The concentration of thiophene in the reac-
tion mixture was 50 ppm. It is apparent from Table 3 that dispersion of the
metals on higher-valence doped carriers has a beneficial influence on the sulfur
poisoning characteristics of the catalysts. This is revealed by the fact that the
 109

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

The resultspresented in the previous section clearly demonstratethat the

adsorptiveand kineticparametersof metalcrystal&es are significantlyaltered
when these are dispersedon TiOz carriersdoped with higher-valencecations.
 111

The directional influence of carrier doping depends on the particular metal.

Thus, the hydrogen adsorption capacity and hydrogenation activity of plati-
num is reduced upon doping of the carrier with higher-valence cations while
the corresponding parameters of Rh, Ru and Pd are enhanced. The magnitude
of alteration of absorptive and kinetic parameters, in all cases, depends on the
concentration of the dopant in the carrier matrix.
The modifications of chemisorptive capacity, intrinsic activity, selectivity
and sulfur tolerance of metal crystallites supported on doped semiconductive
carriers are thought to originate in an electronic interaction at the metal-sup-
port interface which alters the work function of surface metal atoms [ 8-131.
Other possible explanations such as the modification of the degree of disper-
sion of the metal or diffusion of impurities originating from the carrier to the
surface of metal crystallites during catalyst preparation or during reaction have
been eliminated experimentally [ 9,10,12]. The interactions between the metal
crystallites and the support can be explained evoking the theory of metal-
semiconductor contacts. According to this theory, if a metal is in contact with
a semiconductor, at thermodynamic equilibrium the Fermi energy level of the
two solids in contact is at equal height. This implies that electrons are trans-
ferred from one solid to the other, depending on the relative height of the Fermi
levels before contact.
The metal-semiconductor boundary layer model is shown schematically in
Fig. 8, which shows the energy level diagram of the solids, (a) before and (b )
after contact. The barrier shown results from differences in the work function
of the two substances. The energy band diagrams shown in Fig. 8 illustrate the
process of barrier formation. The work function of the metal, CD,,is defined as
the amount of energy required to raise an electron from the Fermi level to the
vacuum level. The vacuum level is the energy level of an electron just outside
the metal with zero kinetic energy. The work function, @,, of the semiconduc-
tor is defined similarly and it is a variable quantity because the Fermi level of
the semiconductor varies with doping. An important surface parameter which

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

1 M. Koussathana, D. Vamvouka, H. Economou and X. Verykios, Appl. CataI., 72 (1991) 283.

2 J.H. Sinfelt, J. Phys. Chem., 68 (1964) 344.
3 W.F. Taylor, D.J.C. Yates and J.H. Sinfelt, Trans. Faraday Sot., 61 (1965) 2044.
4 W.F. Taylor, J.H. Sinfelt and D.J.C. Yates, J. Phys. Chem., 69 (1965) 3857.
5 G.-JM. Schwab, in Advances in Catalysis, Vol. 27, Academic Press, Orlando, Florida, 1978,
p. 1.
6 F. Solymosi, Catal. Rev., 1 (1967) 233.
7 F. Solymosi, I. Tombacz and J. Koszta, J. Catal., 95 (1985) 578.
8 E.C. Akubuiro and X.E. Verykios, J. CataI., 103 (1987) 320.
9 E.C. Akubuiro and X.E. Verykios, J. CataI., 113 (1988) 106.
10 E.C. Akubuiro, T. Ioannides and X.E. Verykios, J. Catal., 116 (1989) 590.
11 EC. Akubuiro and X.E. Verykios, J. Phys. Chem. Solids, 50 (1989) 17.
12 E.C. Akubuiro, X.E. Verykios and T. Ioannides, Appl. Catal., 46 (1989) 297.
13 T. Ioannides and X.E. Verykios, J. Catal., (1991) submitted for publication.