Applied Catalysis, 46 (1989) 269-279

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

269
Influence of the Support on the Catalytic
properties of Nickel/Ceria in Carbon monoxide and
Benzene Hydrogenation
J. BARRAULT* andA. ALOUCHE
Laboratoire de Catalyse en Chimie Organique, UA CNRS 350, 40 Avenue du Recteur Pineau,
86022 Poitiers Cedex (France)
V. PAUL-BONCOUR
Laboratoire de Chimie Metallurgique des Terres Rares, ER CNRS 209, 1 Place Aristide Briand,
92190 Meudon (France)
L. HILAIRE
Laboratoire de Catalyse et Chimie des Surfaces, UA CNRS 423, 4 Rue Blaise Pascal, 67070
Strasbourg Cedex (France)
and
A. PERCHERON-GUEGAN
Laboratoire de Chimie Metallurgique des Terres Rares, ER CNRS 209,1 Place Aristide Briand,
92190 Meudon (France)
(Received 20 June 1988, revised manuscript received 22 September 1988)
ABSTRACT
In this work the catalytic properties of nickel supported on various supports (AI
20:l
, Si0
2
, Ce02)
in syngas conversion are compared. The influence of the temperature of reduction pretreatment
was studied. The characterization of the catalysts was performed by temperature programmed
reduction, isothermal reduction, CO and H
2
chemisorption, X-ray diffraction, X-ray absorption
spectroscopy, magnetization and X-ray photoelectron spectroscopy. The modification of the cat-
alytic properties of Ni/Ce02 catalysts with reduction pretreatment is correlated to the transfor-
mation of the Ce02 support and to strong interactions between these species and metal particles.
INTRODUCTION
Previous work on the catalytic behaviour of intermetallic compounds of rare
earths and transition metals in the syngas reaction showed intermetallic trans-
formation into nickel particles and rare earth oxides [1-4]. Their interesting
catalytic properties led us to prepare catalysts of nickel supported on rare earth
oxides by an impregnation method in order that we might compare them with
Ni/Al
203
and Ni/Si0
2
catalysts.
0166-9834/89/$03.50 1989 Elsevier Science Publishers B.V.
270
TABLE 1
Catalytic properties of nickel in the Co H
2
reaction as a function of pretreatment conditions for
different supports
Ni(7.5%)/ Ce0 2 Ni(11.4%)/Al
203
Ni(8%)/Si0
2
Calcination (0 C) 500 - 500
Reduction (0 C) 250 250 400 400 400 500 500
Reaction (0 C) 250 250 250 400 400 250 250
Activity (X 10
3
) 6 5 0 6 5 54 25
(mole CO h-1g-
1
Ni)
Selectivity (%) 39 37 10 12 41 35
CH
4
C
2-C4
46 52 20 18 44 41
C
5
+ 4 13 13
CO
2
11 11 70 70 2 11
% Olefins
in C
2-C4
37 55 90 90 40 38
The present paper deals with the study of the catalytic properties of Ni/
Ce02 in carbon monoxide and benzene hydrogenation with special emphasis
on the role played by the temperature of the reduction pretreatment.
Characterization of the catalysts by the following physicochemical and
physical measurements is reported: temperature-programmed reduction
(TPR), isothermal reduction, CO and H
2
chemisorption, X-ray diffraction
(XRD ), magnetization, X-ray absorption spectroscopy (XAS) and X-ray
photoelectron spectroscopy (XPS).
A correlation between the change of catalytic properties and the physico-
chemical and physical transformation of the NijCe02 catalyst as a function of
the pretreatment shows the strong influence of the Ce02 support.
EXPERIMENTAL
Samples
The catalysts were prepared by impregnation of an aqueous solution of nickel
nitrate (98%, Fluka) on cerium dioxide (99.9 EGA-Chemie with 20 m
2g- 1
BET area), y-A1
203
(Rhone Poulenc, GFSC with 210 m
2g- 1
BET area) and
Si0
2
(Rhone Poulenc, PBS 300 with 260 m
2g- 1
BET area). After complete
drying on a sandbath the powders were heated in an oven at 393 K for 12 h.
Before use for the catalytic reactions the solids obtained were, in some cases,
calcined at 500
0
C (see Table 1) then reduced with hydrogen in situ at different
temperatures (see Table 1).
Catalytic reactions were performed in a dynamic fixed bed reactor described
in ref. 1. The experimental conditions were as follows:
271
(CO, H
2)
reaction: CO/H
2=1
at 1 atm and T=250C or 400C
(CsH
s,
H
2)
reaction: C
sHs/H2=
1/20 at 1 atm and T=50C.
Characterization methods
TPR and adsorption experiments were carried out using a pulse chromato-
graphic method described previously [2]. Before each TPR experiment, the
samples were outgassed for 2 h at the temperature of reduction, then cooled
down to room temperature. The heating rate was 4C min -1. Hydrogen and
carbon monoxide adsorption were determined on samples reduced for 2 h un-
der hydrogen at a given temperature.
For the following characterizations, the samples were treated as for the cat-
alytic reaction, handled in an argon filled glove box and then sealed either
under argon or under vacuum in an adapted container.
The Debye Sherrer method was used for X-ray powder diffraction
Magnetization measurements were performed on a vibrating magnetometer
in the temperature range 77 620 K and magnetic fields from 0 to 10 kGs.
X-ray absorption data were collected at Lure using the synchroton radiation
provided either by the DCI ring for the Ni-K edge or by the ACO ring for the
CeM
rv_v
edge. EXAFS spectra at the Ni-K edge were collected with a silicon
(311) double crystal monochromator on an EXAFS III device. CeM
rv-v
edge
spectra were collected by photoelectron yield using a double crystal mono-
chromator equipped with beryl crystals [5]. This method allowed us to analyze
a thickness of 100 Aat the surface of the samples.
For the XPS experiments, the samples were dried at 120C and the oxida-
tion and reduction treatments carried out in situ without exposure to air before
analysis. These experiments were carried out in a Vacuum Generators ESCA
III spectrometer using Al Ka radiation (h u= 1486.6 eV).
RESULTS
Catalytic properties
Carbon monoxide hydrogenation
The catalytic properties of Ni7.5/Ce02 submitted to different pretreatments
of calcination and reduction are compared in Table 1with the results for Ni
l1 A
/
A1
203
and Ni
s/Si02
which were not calcined but were reduced at 500C. These
catalytic values were obtained after catalyst stabilization and the product dis-
tributions are compared for similar carbon monoxide conversions ( < 10%).
First we see that the calcination treatment neither changed the activity nor
the selectivity of the Ni/Ce02 catalyst while the temperature of reduction had
a drastic effect: When reduced at 250C, Ni/Ce02 was less active than Ni/
A1
203
and Ni/Si0
2
but exhibited the same products distribution. However, if
272
reduced at 4OOC, Ni/CeOI was not active if the catalytic reaction was per-
formed at 250C and it was necessary to increase this temperature to 400C
to attain the same level of actlvlty as in the previous case. The selectivity was
also very different, with 70~ r of carbon dioxide being produced instead of 10%
and 90% of olefins in the C C a fraction.
Benzene hydrogenation
The activity of the catalvsts 1s given in Table 2. When reduced at 250C
Ni/CeO, exhibited slightlv greater activity than the other two catalysts. But,
as for the previous reactron. reduction at 400 C induced deactivation of the
Ni/CeO, catalyst.
Characterization
The study of the catalvtir properties of Ni- J CeO, showed that the temper-
ature of reduction plays a verv I mportant role whereas calcination treatment
has no effect in this range of concentration. So we selected for characterization
the two samples with the most different properties i.e. Ni7.s/Ce02 reduced at
250 and 400 C respectivelc However, the samples with A1203 and SiO, sup-
ports and CeO, alone are compared with the catalysts to show the differences
in reducibility (TPR) and chemisorption behaviour.
TPR
The results for the three catalysts (nickel supported on CeO,, A1203, SiOz)
and for CeO, alone are presented in Fig. l* It appears that nickel is reduced at
a lower temperature when I t is deposited on CeO, than on the other supports
and the time of reduction I S shorter : hydrogen uptake became very important
from 300 C and decreased from 400 C. The reduction stopped after about 40
min in this range of temperature. I n contrast, on SiO, and A1203 supports the
reduction began at 350 and 450 C respectively with a broad maximum at 450
and 550C respectively. However, for CeO,> alone the hydrogen uptake began
TABLE 2
Catalytic activity of nickel in benzene hvdrogenation as a function of the temperature of reduction
pretreatment for different supports
Ni(7.Fii 4 (CO Ni(11.4%)/ Ni(3.7%)/SiO,
AI ,O,)
Temperature of
reduction ( C )
Activity (X 10)
(mole C,H,
h-g-Ni)
250 400 500 500
5.5 I ! 0;3 4.8 4.6
273
T(C) Time (mn)
Fig. 1. Temperature programmed reduction of nickel on different supports precalcined at 500 a C,
(0) Ni(i.Swt.-%)/CeO, (m) Ni(8wt:%)/SiO, (A) Ni(ll.4wt.-%)/Al,O,andofCeO, (*).
TABLE 3
Reducibility of nickel supported by different oxides at constant temperature
Ni(7.5%)/CeO, Ni(ll.4%)/AlL0.1 Ni(8%)/SiOT CeO,
Temperature
of reduction 250 400 500 500 500 800
pretreatment ( C )
Percentage of
reduction 126 132 92 97 0 3
only from 500 c C with one maximum around 620 o C and a second, broader one
around 800 c C.
I sothermal reduction
The reduction rate of the catalysts during treatment for 10 h under 1 atm of
hydrogen at a constant temperature is given in Table 3.
For Ni,,,/CeOz the reduction rate was about the same, independent of the
temperature of reduction and was higher than loo%, whereas, on the other
supports nickel was not completely reduced during the same time at 500C.
We deduced therefore, that for Ni,_,J Ce02 it is necessary to take into account
the reduction of the CeO, support from 250 C. From the percentage of reduc-
tion, with the hypothesis that all the nickel is reduced, we obtained the follow-
ing stoichiometry for the support after reduction: CeO, at 250C and
CeO,.,,.,.,, at 400C.
We note that, as in the TPR experiment, CeO, alone did not take up hydro-
gen before 500C. Therefore, CeO, is more easily reduced in the presence of
nickel.
Ni
71-Ce02
-v
_-c--
_a--- co
,/-
,/
,
Fig. 2. Effect of reduction temperature on hydrogen and carbon monoxide adsorption on Ni/CeO,.
The reduction time is 2 h.
TABLE 4
Hydrogen and carbon monoxide chemisorption of catalysts and dispersion of nickel (0% ) as a
function of the temperature of reduction (T,)
Ni(7.5%)/CeO, Ni(11.4%)/Al,O:, Ni(8%)/SiO,
Ta ((2) 250 400 500 500
pmole CO g _ I cat 17 37 119 80
D (s) 1.3 2.9 6.1 6
,umole H,g- I cat 10 0.5 117 42
D (%I 0.8 0.04 6 6.1
Hydrogen and carbon monoxide chemisorption
The variation of carbon monoxide and hydrogen chemisorption on Ni7,5/
CeO, as a function of the temperature of reduction is reported in Fig. 2. As the
temperature increased, the carbon monoxide chemisorption increased, whereas
hydrogen chemisorption vanished at 350C. This contrasting behaviour did
not allow us to deduce the number of active sites for the CeO, support as for
the SiO, and A1203 supports. Indeed, the dispersions calculated for the three
catalysts are summarized in Table 4: good agreement was obtained for the
number of moles chemisorbed and the calculated dispersion of the metal, what-
ever the gas, for the SiO, and Al,O, supports, whereas for the CeOz support
there was no correlation between the two sets of values.
XRD
For both compounds, i.e. Ni,,,/ CeO, reduced at 250 and 400C narrow dif-
fraction lines were obtained and all of them were indexed as CeOz and nickel
metal.
Magnetization
Field cooled magnetization curves were measured between 77 and 620 K. For
both samples (i.e. NiJCeO, reduced at 250 C and 400C ), below 500 K pro-
275
TABLE 5
Saturation magnetization (M,) and percentage of nickel deduced from M, and chemical analysis
for Ni/CeO, samples
Compounds M, (300 K) wt.-% Ni
(emu)
deduced from M,
yt.-% Ni
deduced from chemical
analysis
Ni(7.5%)/CeO,
reduced at
250C
Ni(7.5%)/CeO,
reduced at
400C
0.787 8.4 7.5
0.916 7.3 7.5
gressive spin freezing of nickel particles was evidenced by the observation of a
remanent magnetization and a deviation of the magnetic susceptibility from
the Curie Weiss law [ 61. The following results are detailed in ref. 6. The weight
of nickel deduced from chemical analysis and saturation magnetization are in
good agreement for both compounds within a 10% experimental error (Table
5 ). Moreover, the Curie temperatures were very close to those of nickel metal.
This shows that at both 250 and 400 o C the nickel was completely reduced.
The particle size distribution (Fig. 4 in ref. 6) showed little difference be-
tween the two samples. Most particles had a mean size of between 7 and 10 nm
for both samples. However increase of the reduction temperature leads to a
redistribution of the particle mean size, the major part of the nickel particles
have a size around 8 nm, but some of them have a size larger than 13 nm.
The distribution of particles with diameters smaller than 7 nm was not in-
vestigated. I ndeed, measurements in the range 4.2 K -=z T< 77 K only showed
that the remanent magnetization saturated below 70 K and that the magneti-
zation n-versus-external magnetic field curves M (H ) become temperature in-
dependent within 1%. Therefore, the total number of particles with dimensions
in the range d, (4.2 K) <d < d, (70 K) i.e. 1 cd,< 7 nm represents less than
1% of the total number of particles.
The specific area calculated from the particle size distribution was the same,
within a few percent, for the two samples: 21 m2gg1 catalyst. This shows that
for this relatively high concentration of active metal, the specific area retains
the initial value of the support.
X-ray absorption
EXAFS spectra collected at the Ni-K edge for Ni/CeO, catalysts were ana-
lyzed according to a method described elsewhere [ 7 1. The normalized EXAFS
oscillations contain information concerning the number and the nature of the
nearest neighbouring atoms and their distances to the studied central atom.
Fig. 3 shows that the spectra of the two samples of Ni/CeO, and nickel metal
276
-0.09
0 200 400 600
E(eV)
Fig. 3. EXAFS spectra at the Ni-K edge of Ni/CeOa reduced at 250 and 400C and the nickel
reference.
TABLE 6
I nfluence of the oxidation and reduction treatments on the surface composition, elemental binding
energies of components and cerium valency
Treatment Ni(Ni+Ce)
E Ni2p3,Y
at(%)+5%
(eV)
Cevalency
Main peak Small peaks
Driedat 120C 63 855.6 3.34
Oxidation (O,, 500 C) 58 854 855.6 3.27
Reduction (H,, 25OC) 68 852.7 854 3.27
Reduction (H2, 400C) 50 852.5 3.16
are exactly superimposed. This means that large nickel particles were present
in both cases.
The spectrum at the Ce Mrv_v edge of the sample reduced at 250 C was
identical to that of the other sample and to the CeO, spectra [B].
XPS
The influence of the oxidation and reduction treatments on the surface com-
position of the samples and the electronic state of the constituents are sum-
marized in Table 6. Binding energies of Ni2p3,2 and Ce3d5,2 peaks were calculated
with a precision of t 0.2 eV to determine the nickel and cerium electronic state.
The relative spectral weight of Ce3+ -Ce4+ states (valency) was deduced by
a method described elsewhere [9]. The surface compositions were estimated
277
A
655.6
I
Ni 2p3* 873.5
I
a
854
&
zi
652.5 ,
t
c
k_
d
E(eV)
Fig. 4. Evolution of the Ni 2p photoemission spectra of Ni/CeO, as a function of pretreatment.
(a)Driedat 120C; (b) oxidizedat 500C; (c) reduced at 25OC (d) reduced at 400C.
from the area of the photoelectron peaks. The evolution of the photoelectron
peaks of nickel is shown in Fig. 4. Drying of the Ni/CeO, sample resulted in a
peak at 855.6 eV (Fig. 4a) which was ascribed to nickel nitrate. I ndeed the
whole spectrum of cerium was characteristic of CeO, [9].
After oxidation at 500C (Fig. 4b), the nickel was almost completely oxi-
dized (854 eV) with only a small amount of nitrate (855.6 eV) present. The
cerium remained as CeO, with a slight decrease of the valency. After reduc-
tion at 250C (Fig. 4c), the nickel was almost completely reduced (852.7 eV)
to the metal, with a small contribution from nitrate and oxide. Cerium re-
mained in the same state as after oxidation. After reduction at 400 C (Fig. 4d)
the nickel was completely reduced to the metal (852.5 eV) and the valency
of cerium decreased to 3.16 showing the presence of Ce3+ species. However,
these species were present only in small amounts, since we could not resolve
any transition around 885 eV which was characteristic of Ce3+.
The change of the percentage of nickel at the surface depending on the var-
ious treatments was not determined with accuracy, however it is noteworthy
that the mean value, around 55 wt.-%, is quite high compared to the bulk value
of 7.5 wt.-% (17.3 at.-% ) showing an important nickel enrichment of the sur-
face. Moreover a relative decrease of about 25% was observed between the
samples reduced at 250 SC and 400 3 C respectively.
DI SCUSSI ON
We have shown that nickel supported on CeO, exhibits different behaviour
from that which is observed with Al,O, and SO, supports.
Firstly, concerning the reducibility, nickel on CeO, was reduced at a lower
temperature and the hydrogen uptake showed partial reduction of the CeO,
support leading to a nonstoichiometric oxide in addition to the reduction of
nickel. I ndeed, unlike Al,O, and SiOr, CeO, is a reducible oxide. The TPR
experiments on CeO, alone show two hydrogen uptake peaks at 600 and 800 C,
which agreed with the results of Yao and Yu Yao [lo] who associat.ed them
with the reduction of surface capping oxygen and bulk oxygen anions respec-
tively. Moreover, these authors observed a lowering of the reduction temper-
ature of CeO, in the presence of precious metals as for nickel. I nversely, the
reduction of NiO was easier in the presence of CeO,.
Secondly, we showed that the catalytic properties of Ni/CeO, depended
mainly on the temperature of reduction pretreatment. After a 250 C treatment
Ni/CeO, exhibited the same catalytic behaviour as Ni/Al,O, and Ni/SiO, re-
duced at 500 s C : the selectivities were the same, and the difference in activities
could be ascribed to the difference of the specific area of the supports and
consequently to the lower dispersion of the metal (Table 4). I ndeed the char-
acterizations showed that, for the three catalysts, nickel was almost completely
reduced in each case.
Deactivation of the Ni/CeO, catalyst reduced at 400 C was observed for the
two catalytic reactions, although the specific area of nickel deduced from mag-
netic measurements was unchanged and the bulk characterizations (XAS,
XRD) did not allow us to detect a difference between the two samples pre-
treated at 250 and 400 C respectively; only Ni and CeO, were identified. How-
ever the chemisorption and XPS experiments, sensitive to the surface, showed
important differences: An increase of carbon monoxide chemisorption was ob-
served as the temperature increased whereas hydrogen chemisorption de-
creased. The nickel concentration at the surface, determined by XPS, showed
a decrease of about 25% between the sample reduced at 250 and that reduced
at 400 C. I n addition, a decrease of the oxidation state of cerium by reduction
at 400 0 C was shown at the surface.
A similar effect of the reduction temperatures on catalytic properties has
been observed for other transition metals supported on reducible oxide cata-
lysts such as TiO, or ZrO, [ 11, 121, and is known as strong metal-support
interaction (SMSI ) [ 111. I n fact, some characteristics of Ni/CeO, resemble
those of Ni/TiO+ reduction of the TiO, support led to the formation of Ti,07
with the presence of Ti+ species [ 13,141 and the hydrogen and carbon mon-
oxide chemisorption changed as the temperature increased.
I n order to explain this behaviour, some authors suggest a migration of the
reduced species of the support on the transit.ion metal [ 15, 161 leading to the
creation of new active sites. Thus the chemisorption properties of the transi-
tion metal would be modified by the interaction wit.h the reduced species of the
support.
This mechanism seems to be in agreement with our observations. When the
279
reduction temperature increased we showed, by XPS, an increase in the re-
duction of cerium at the surface (creation of Ce+ species) and a decrease in
the nickel concentration which should correspond to the presence of the oxide
species CeO, _ r on the surface of the nickel particles.
Moreover, the lowering of the hydrogen chemisorption could be explained
by a decrease in the accessible nickel surface. As for the increase in the carbon
monoxide chemisorption, it could be due to carbon monoxide adsorption on
CeO,_,, followed by a large desorption of carbon dioxide which was observed
in the products of the reaction of carbon monoxide hydrogenation at 400C
with the 400 C reduced Ni/ CeO,.
In conclusion, we have shown the influence of the temperature of the reduc-
tion pretreatment on the catalytic properties of nickel supported on ceria. An
increase in this temperature induced deactivation of the catalysts in carbon
monoxide and benzene hydrogenation. This deactivation is ascribed to a mod-
ification of the active sites with a strong interaction occurring bet.ween the
nickel and the reduced species present at the surface of the support, since no
change of the specific area was observed.
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