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Applied Catalysis A: General 237 (2002) 263–273

V2 O5–SmVO4 mechanical mixture: oxidative


dehydrogenation of propane
Bibiana P. Barbero, Luis E. Cadus∗
Instituto de Investigaciones en Tecnologı́a Quı́mica (INTEQUI), UNSL—CONICET,
Casilla de Correo 290, 5700 San Luis, Argentina
Received 3 January 2002; received in revised form 5 June 2002; accepted 8 June 2002

Abstract
V2 O5 , SmVO4 and the mechanical mixtures of them in two different mass ratios were studied in the reaction of oxidative
dehydrogenation of propane to propene. The results of the catalytic activity indicate the presence of a synergy effect in the
yield to propene at reaction temperatures lower than 450 ◦ C. This synergy effect disappears when the reaction temperature
increases. When the catalysts tested at 500 ◦ C were re-evaluated at low temperatures (350–400 ◦ C), a significant decrease in
yield to propene was observed. By the results of physicochemical characterization (BET, X-ray diffraction (XRD), temperature
programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS)), it can be inferred that the synergy would be due
to a transient state of the catalytic system. In it, surface vanadium species adsorbed on the SmVO4 and originated by V2 O5
migration would constitute active and selective centers for the oxidative dehydrogenation of propane. The reason for the loss
of synergy when the reaction temperature increases would be that the transformation of the catalytic system continues towards
the coverage of SmVO4 phase by V2 O5 . Thus, the surface of SmVO4 is covered by conglomerates of surface VOx species
and even recrystallized V2 O5 . This surface transformation modifies the catalytic performance of the system.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Oxidative dehydrogenation of propane; Vanadium pentoxide; Samarium orthovanadate; Mechanical mixtures; Synergy effect

1. Introduction An attractive alternative to the classical dehydrogena-


tion would be the oxidative dehydrogenation. In this
The transformation of alkanes into useful interme- process the hydrogen abstracted is oxidized and the
diates is currently the object of intense investigations absolute heat of reaction is sensibly reduced. There-
in the field of catalysis. It is possible to obtain alkenes fore, the process becomes significant at a much lower
from short chain alkanes by catalytic dehydrogenation. reaction temperature.
However, the dehydrogenation of the alkane to give The vanadia-based systems are active and selective
the corresponding alkenes and H2 is a strongly en- in various types of hydrocarbon oxidation reactions
dothermic process which has to be carried out at tem- comprising: (a) oxidative dehydrogenation of alka-
peratures >600 ◦ C. At these high reaction temperatures nes and alkenes and (b) reactions with formation of
needed, other unwanted reactions leading to coke also the oxygenated products. The V-Mg-O catalysts have
occur, and the catalyst needs frequent regeneration. been proposed to be active and relatively selective
in the oxidative dehydrogenation of propane and bu-
∗ Corresponding author. Fax: +54-2652-426711. tane [1–11]. Three Mg vanadate phases were found to
E-mail address: lcadus@unsl.edu.ar (L.E. Cadus). form in V-Mg-O catalysts as a function of vanadium

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 3 3 6 - 8
264 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273

concentration and calcination temperature [3]. Kung and citric acid (Mallinckrodt) were used as reagents.
and co-workers attributed the active phase to mag- An aqueous solution of citric acid with a 10% ex-
nesium orthovanadate (Mg3 V2 O8 ) [2], but Volta and cess over the number of ionic equivalents of cations
co-workers suggested that magnesium pyrovanadate (three ions per molecule of citric acid) was pre-
(␣-Mg2 V2 O7 ) was the active phase and Mg3 V2 O8 pared. The aqueous solution of Sm(NO3 )3 ·6H2 O
was responsible for total oxidation [3]. Further, Gao was added to that of citric acid and it was agitated
et al. prepared three pure phases of magnesium vana- for 30 min. Then the aqueous ammoniacal solution
dates and confirmed that in the oxydehydrogenation of NH4 VO3 was added and agitated for 30 min.
of propane, ␣-Mg2 V2 O7 was the most selective and The amounts of Sm(NO3 )3 ·6H2 O and NH4 VO3
MgV2 O6 was the worst [6]. It must be noted from used, corresponded to the molar ratio Sm:V = 1:1.
those studies [2,3] that in their V-Mg-O working cat- The resulting solution was concentrated by evap-
alysts, at least two phases have been identified simul- orating water slowly in vacuum in a rotavapor at
taneously. Thus, it is reasonable to suspect that the 70 ◦ C until a gel was obtained. This gel was dried
overall catalytic behavior should not be attributed to in a vacuum oven at 70 ◦ C overnight. The result-
just one phase. In fact, Gao et al. also found that the ing solid was ground and then heated slowly up
coexistence of ␣-Mg2 V2 O7 or MgO with Mg3 V2 O8 to 400 ◦ C in order to decompose the organic pre-
in intimate contact could promote the selectivity to cursor, and then it was calcined at 600 ◦ C for
propene of Mg3 V2 O8 [11]. 3 h.
In many other cases, it has been found that the
catalytic properties of the multiphasic catalysts are 2.1.2. V2 O5 –SmVO4 mechanical mixtures
remarkably different from those of the individual Mechanical mixtures of separately prepared V2 O5
constituents. Activity and/or selectivity enhancement, and SmVO4 were obtained with different SmVO4 con-
which has been observed when two phases are present, tents. The corresponding powders were dispersed and
is of wide interest [11–14]. On the other hand, few mixed in n-pentane with the help of an ultrasonic de-
examples, have been reported about the catalysts vice and were subsequently evaporated under reduced
preparation for oxidative dehydrogenation of propane pressure at room temperature to remove the solvent.
by replacing magnesium with rare earth [15–19], al- The solid was dried at 100 ◦ C during 12 h. No further
though some rare earth orthovanadates have shown calcination was carried out in the resulting mechanical
to be almost as selective as the magnesium vanadates mixtures. The samples with 8.5 and 31.5 wt.% SmVO4
for the oxidation of butane [20]. In this paper, the are referred as mmSmV8.5 and mmSmV31.5, respec-
preparation and the physicochemical characteriza- tively.
tion of the mechanical mixtures containing different
amounts of SmVO4 and V2 O5 is reported. In addi- 2.2. Catalyst characterization
tion, a synergy cooperation between the two phases
in the oxidative dehydrogenation of propane at low 2.2.1. Specific surface area measurements (BET)
reaction temperature is shown. Specific surface areas (SSA, m2 /g) were determined
from nitrogen adsorption isotherms at 77 K by the
BET method. Samples were previously outgassed in
2. Experimental vacuum at 200 ◦ C. A Micromeritics Accusorb 2100E
apparatus was used.
2.1. Catalyst preparation
2.2.2. X-ray diffraction (XRD)
2.1.1. Pure oxides: vanadium pentoxide and XRD patterns were obtained by using a Rigaku
samarium orthovanadate diffractometer operated at 30 kV and 25 mA by
V2 O5 was prepared by calcination in air of NH4 VO3 employing Ni-filtered Cu K␣ radiation (λ =
(Mallinckrodt) at 450 ◦ C for 4 h. 0.15418 nm). The crystalline phases were identi-
SmVO4 was prepared by the citrate method [21]. fied by reference to the powder diffraction data
Sm(NO3 )3 ·6H2 O (Fluka), NH4 VO3 (Mallinckrodt) (JCPDS-ICDD).
B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273 265

2.2.3. Temperature programmed reduction (TPR) hydrocarbons and CO2 and a Carbosphere column for
The temperature programmed reduction was carried carbon monoxide, methane and oxygen were used. The
out in a quartz U-type tubular reactor using a TCD as homogeneous contribution was tested in the empty re-
a detector. A 20 mg sample without any previous treat- actor. These runs showed no activity <550 ◦ C. The
ment was used. The reducing gas was a mixture of results were very similar with and without the use of
4 vol.% H2 /Ar at a total flow rate of 50 ml/min. Tem- quartz particles.
perature was increased at a rate of 15 ◦ C/min, from The conversion and selectivity for products were
room temperature to 900 ◦ C. The temperature was kept defined as follows:
constant at 900 ◦ C until the signal of hydrogen con- Selectivity for product i, (Si ) is given by
sumption returned to the initial values. y i ni
Si = 
yi ni
2.2.4. X-ray photoelectron spectroscopy (XPS)
An VG ESCA III equipment was used. The radi- Conversion of propane, XC3 H8 , is given by
ation K␣ of Mg was its non monochromatic X-ray 
yi ni
source. The source was operated at 11 kV and 20 mA. XC3 H8 = 
(yC3 H8 nC3 H8 + yi ni )
A 20 eV pass energy was used. Spectra were registered
after purging the samples at room temperature in vac- where yi and yC3 H8 are the mole fractions of product
uum (10−9 Torr) overnight. The fine-powder samples i and propane, respectively; and ni and nC3 H8 are the
were prepared in the form of pellets and were pressed number of carbon atoms in each molecule of prod-
at 25 kN/cm2 . The charging effect was corrected with uct i and propane, respectively. All terms were to be
reference to C 1s binding energy at 284.8 eV. Spec- evaluated for the exit stream. The carbon balance was
tra were deconvoluted with an appropriate software. found to be ±4%.
Surface atomic ratios were estimated by the corre-
sponding peak area ratios using the effective ioniza- 3. Results
tion cross-section values tabulated by Scofield [22]
and also making corrections based on the number of 3.1. Specific surface area (BET)
scans and the characteristic kinetic energies of the an-
alyzed elements. In Table 1, the specific surface areas (SSA) ob-
tained with pure phases and mechanical mixtures are
2.2.5. Electron paramagnetic resonance (EPR) shown. The areas of the mechanical mixtures are in
Spectra were obtained using a Bruker ESP 300 good agreement with the expected theoretical values
Spectrometer operated at X-band at a temperature of defined as:
120 K. Resulting spectra were treated with a specially
(wt.% V2 O5 ) · SSAV2 O5
designed software.
+(wt.% SmVO4 ) · SSASmVO4
SSAtheoretical =
100
2.3. Catalytic test
After the catalytic test, V2 O5 specific surface area de-
The catalysts (1 g, 0.5–0.8 mm particle diameter) creases strongly (41%), the surface areas of mechani-
were tested in a fixed bed, quartz tubular reactor oper- cal mixtures decrease about 25% and that of SmVO4 ,
ated at atmospheric pressure. The temperature, mea- practically does not change.
sured with a coaxial thermocouple, varied between
350 and 500 ◦ C. The feed was a mixture of 4 vol.% 3.2. X-ray diffraction (XRD)
propane, 4 vol.% oxygen, and balanced with helium.
The flow rate was 100 ml/min at room temperature. The XRD results of mechanical mixtures before the
The reactants and reaction products were alternately catalytic test are shown in Fig. 1. They indicate the
analyzed on-line by a Shimadzu GC9A gas chromato- presence of V2 O5 and SmVO4 and there is no evidence
graph equipped with a thermal conductivity detector. of new phases. The intensities of signals correspond-
A Porapaq Q (80–100 mesh) column for separating ing to each phase are proportional to the composition.
266 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273

Table 1
Specific surface area (m2 /g) of pure phases and mechanical mixtures compared with theoretical values
Before the catalytic test After the catalytic test

Experimental Theoretical Difference (%) Experimental Theoretical Difference (%)

V2 O5 5.84 – – 3.43 – –
mmSmV8.5 7.47 7.82 4.47 5.66 5.54 −2.17
mmSmV31.5 12.44 13.16 5.45 9.15 11.24 18.56
SmVO4 29.04 – – 28.18 – –

Fig. 1. XRD of pure phases and mechanical mixtures.

Fig. 2. XRD of the mmSmV31.5 catalyst both fresh and used. (䊉) V2 O5 (JCPDS 41-1426), (+) SmVO4 (JCPDS 17-876).
B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273 267

Table 2
Hydrogen consumption (ml H2 /gcat ) from TPR
Catalysts Experimental Theoretical
V2 O5 235 –
mmSmV8.5 213 222
mmSmV31.5 206 190
SmVO4 91 –

Tmax of the first two peaks shifts towards higher tem-


peratures, and (b) the Tmax of the last reduction stage
shifts to lower temperatures.
Hydrogen consumption per weight of catalyst
(Table 2) decreases from V2 O5 to SmVO4 . The re-
sults obtained for the mechanical mixtures are in
good agreement with the theoretically estimated val-
ues based on the results of hydrogen consumption of
pure phases.

3.4. X-ray photoelectron spectroscopy (XPS)

Table 3 shows XPS results. The V 2p3/2 /Sm 4d sur-


face atomic ratio of mmSmV31.5 catalyst increases
from approximately 6 to 11.6 by effect of the catalytic
Fig. 3. TPR profiles of the catalysts. test. To discriminate between the effect of temperature
and of reaction atmosphere, the mmSmV31.5 sample
As an example, Fig. 2 shows the XRD patterns of the calcined at 550 ◦ C without undergoing catalytic test
mmSmV31.5 catalyst both fresh and used. After the conditions was analyzed. The results indicate that the
catalytic test, the same phases are present, although a surface enrichment in vanadium observed in the sam-
relative decrease of V2 O5 signal intensity in compar- ple after the catalytic test occurs mainly under reaction
ison to that of SmVO4 is observed. conditions.
No shift in values of V 2p3/2 binding energies by
3.3. Temperature programmed reduction (TPR) reaction test is observed.

TPR results are shown in Fig. 3. The reduction curve 3.5. Electron paramagnetic resonance (EPR)
of V2 O5 presents three reduction stages. The temper-
atures of maximum hydrogen consumption, Tmax , are Neither fresh nor used SmVO4 prepared by the cit-
at 653, 698, and 895 ◦ C. The last reduction stage is rate method with stoichiometric ratio (Sm:V = 1:1)
completed during the heating period at constant tem-
perature (900 ◦ C). Table 3
Pure SmVO4 presents a TPR curve which indicates Binding energy and V/Sm surface atomic ratio from XPS
that there would be a single reduction stage. However, V 2p3/2 / Binding energy (eV)
there could be more than one non-resolved stage un- Sm 4d
V 2p3/2 Sm 4d
der experimental conditions used in these studies. The
maximum of this peak is at 760 ◦ C. mmSmV31.5 before the 5.98 517.5 133.7
catalytic test
The reduction curves of the mechanical mixtures mmSmV31.5 after the 11.56 517.4 133.4
result from the contribution of constituent phases ex- catalytic test
hibiting some differences. As SmVO4 proportion in- mmSmV31.5 calcined 5.77 – –
creases in the mixture two phenomena happen: (a) the at 550 ◦ C
268 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273

Fig. 4. EPR results of mmSmV31.5 catalyst both before and after the catalytic test.

present any signal. V2 O5 presents a signal correspond- 3.6. Catalytic activity


ing to V4+ with a g-factor value of 1.972. Both me-
chanical mixtures present EPR signal with a g-factor Figs. 5–7 show the results of catalytic activity. The
value equal to that of V2 O5 . Signal intensity of me- major products were propene, CO and CO2 . Other
chanical mixtures decreases as SmVO4 proportion in oxygenated products were not found. Curves of se-
the sample increases. When spectra of fresh samples lectivity to C3 H6 as a function of C3 H8 conversion of
are compared with those of the samples after the cat- mechanical mixtures (Fig. 5) present the same decreas-
alytic test, a decrease of signal intensity is observed ing form as that of V2 O5 . Conversely, SmVO4 curve
(Fig. 4). decreases slightly as conversion of propane increases.

Fig. 5. Selectivity to propene as a function of the propane conversion on (䊏) V2 O5 , (䊊) mmSmV8.5, (䉫) mmSmV31.5 and (䉲) SmVO4 .
B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273 269

Fig. 6. Propane conversion as a function of the reaction temperature on (䊏) V2 O5 , (䊊) mmSmV8.5, (䉫) mmSmV31.5 and (䉲) SmVO4 .

This indicates that when V2 O5 or SmVO4 is used, tures (350 and 400 ◦ C) but it disappears at 450 ◦ C.
the consecutive combustion of propene on SmVO4 is At higher reaction temperatures (500 ◦ C) the yield to
slower than that on V2 O5 . Fig. 6 shows propane con- propene of mechanical mixtures is lower than that of
version as a function of reaction temperature. A syn- pure phases. The mechanical mixtures tested at 500 ◦ C
ergy effect on the mechanical mixtures can be inferred. were re-evaluated. An important decrease in the yield
Taking in account the yield to propene (Fig. 7), this to propene at low reaction temperatures (350–400 ◦ C)
synergy effect is observed at low reaction tempera- was observed.

Fig. 7. Propene yield as a function of the SmVO4 content at different reaction temperatures: (䊏) 350 ◦ C, (䊉) 400 ◦ C, (䉱) 450 ◦ C and
(䉲) 500 ◦ C.
270 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273

4. Discussion During the preparation step of mechanical mixtures


the possible contamination between the constituent
Most of active and selective catalytic systems in re- phases was avoided. The original phases of mechanical
actions of propane oxydehydrogenation are multipha- mixtures were prepared separately. During the mixing,
sic. In general, these phases are interdispersed and the the temperature was never higher than 70 ◦ C and the
presence of arrangements within the detection range of solvent used was a non-polar compound. According to
the used characterization techniques is not evident. In these considerations, it seems reasonable to expect that
a previous work [23], the evolution of Sm-V-O system mmSmV fresh catalysts result to be constituted by the
by a solid state reaction was studied. Artificially, V2 O5 two well-defined original phases without interaction or
was contaminated with different amounts of samarium contamination between them. The characterization of
by using the technique of impregnation. The detected fresh mechanical mixtures suggests that the nature of
phases corresponded to SmVO4 and V2 O5 . The cat- the constituted phases is not affected during the prepa-
alytic performance of the impregnated catalysts did ration step, this corroborates the previous assumption.
not be different from that of pure V2 O5 due to that In fact, the results of BET specific surface area of fresh
the surface becomes enrichment in vanadium. Many mechanical mixtures are in good agreement with the
works reported in the literature mention synergy ef- expected theoretical values. This would indicate that
fects between the phases present in a catalyst [11–14]. the specific surface area of mixtures is the result of the
However, there is no agreement on whether such syn- contribution of each one of the phases. A solid state
ergy effect is the result of cooperation between the reaction, improbable at synthesis temperature, would
phases or it is simply due to the formation of arrange- cause modifications in the specific surface area. The
ments with a catalytic behavior different from that diffractograms of mechanical mixtures show the char-
of pure phases. The catalytic evaluation of mechani- acteristic lines of the two original phases, V2 O5 and
cal mixtures of V2 O5 and SmVO4 presents interesting SmVO4 , with intensities proportional to the composi-
points to be enhanced. In fact, the catalytic perfor- tion. No new phase was detected. Numerous reported
mance of mechanical mixtures is not the simple con- studies [11,13,14] on mechanical mixtures prepared in
tribution of the phases which constitute the mixtures. similar conditions have not detected either new phases
While V2 O5 exhibits a high selectivity to propene at or contamination between the original phases.
low conversions of propane and this selectivity de- The reaction temperature is relatively high and the
creases markedly as the conversion increases, SmVO4 XPS results proved that the reacting atmosphere con-
presents a relatively good selectivity to low conversion tributes to the redefinition of the surface. In order to
levels which is maintained as the conversion increases understand the behavior of this system, it is very im-
(Fig. 5). This simple observation leads to the conclu- portant to compare the characterization results before
sion that when the pure phases (V2 O5 or SmVO4 ) are and after the catalytic test. In fact, the XRD results
used, the side reactions considered in the ODH re- of used samples compared with fresh ones indicate a
action mechanism [24] proceed at different reaction relative increase in the intensity of lines correspond-
rates. In both mechanical mixtures, there is a similar ing to SmVO4 with respect to those of V2 O5 (Fig. 2).
behavior to that observed on V2 O5 . This would indi- This gives an insight that there is a modification of the
cate that, as with V2 O5 , the consecutive combustion system during the reaction, although the appearance
of propene occurs fast. of new phases was not observed. It could be assumed
The first significant observation about catalytic that SmVO4 crystallinity increases and, therefore, its
performance is that, at reaction temperatures of signal becomes more intense. However, this hypoth-
350 and 400 ◦ C, the yield to propene obtained with esis is difficult to support considering that SmVO4
V2 O5 –SmVO4 mechanical mixtures is higher than was calcined at 600 ◦ C for 3 h during its preparation
that expected by the contribution of each individual and that the reaction temperature was not higher than
phase while at 500 ◦ C, it is lower. The fact that the 500 ◦ C. Other possible explanation of the phenomenon
synergy effect disappears as the reaction temperature observed by XRD could be that the V2 O5 phase be-
increases is not consistent with the other researchers’ comes more amorphous and, thus, its signal inten-
observations [13]. sity decreases. The measurements of specific surface
B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273 271

area show interesting hints to determine what has oc- V2 O5 /TiO2 catalysts, a TPR peak at Tmax ≈ 500 ◦ C
curred. BET specific surface area of V2 O5 decreases is observed [25].
strongly after the catalytic test while that of SmVO4 Although new TPR peaks which would explain the
practically does not vary. It is also important to note decrease of V2 O5 crystallinity with the increase of
that after the catalytic test, the specific surface area SmVO4 content are not observed, a new surface ar-
of the mmSmV31.5 mixture is quite lower than the rangement can be assumed from the interaction be-
expected theoretical specific surface area, i.e. it de- tween phases. This new surface arrangement should
creases more than what was foreseen by effect of the facilitate the contact between the phases in order to
reaction. In mmSmV31.5 sample, an important part that the mentioned interaction occurs. The techniques
of the surface area is supplied by the SmVO4 phase. of massive characterization have given hints of the
This effect is not so evident in mmSmV8.5 catalyst changes which would explain the catalytic behavior.
in which the surface area supplied by SmVO4 is less In order to know what the supposed changes of the
important. surface arrangement are like, surface techniques were
These observations indicate that the process by used. Measurements of mmSmV31.5 sample surface
which V2 O5 crystallinity decreases gives rise to a composition by XPS before and after the catalytic test
deep reformulation of the catalyst capable of affecting were carried out. It was found that V 2p3/2 /Sm 4d
its textural characteristics. surface atomic ratio changes from approximately 6 in
Assuming that no technique can provide by itself the the fresh sample to 11.6 in the used one. This result
information necessary for elucidating this situation, a clearly indicates that there is a vanadium surface en-
combination of TPR, XRD and XPS has been used. richment during the reaction. As it has been reported
The TPR profiles measured for the mechanical mix- in the literature [26], V2 O5 has the capacity to migrate
tures showed that the reduction curves result from on the surface of other solids enveloping them with a
the contribution of the two original phases. However, thin overlayer. However, it is in doubt whether the ef-
some differences are not negligible. As SmVO4 con- fect is due to the temperature or to reaction atmosphere
tent in the mechanical mixtures increases, the Tmax of conditions. To discriminate between the effect of tem-
the first two reduction stages shifts to higher temper- perature and the reaction atmosphere, mmSmV31.5
atures. It would indicate that the interaction between mechanical mixture was analyzed by XPS after cal-
the phases makes the reduction of these stages more cinating it at 550 ◦ C. The results indicate that the re-
difficult, while the reduction of the last stage of V2 O5 action test plays a key role in the reformulation of
is facilitated by the presence of SmVO4 . By XRD it the catalytic surface. Taking in account that water is
was determined that the first reduction stage of V2 O5 a reaction product in the oxidative dehydrogenation
corresponds to V5+ transformation into a mixture of of alkanes, this observation is in agreement with pub-
V5+ to V4+ and the second stage, into the complete lished studies on the influence of the moisture in the
reduction to V4+ . At the end of the reduction process migration of vanadium oxide and molybdenum oxide
all the vanadium is V3+ [23]. As SmVO4 content in [27–29].
the mechanical mixtures increases, a greater shift of Taking into consideration the Tamman temperature
the reduction peaks is observed. Although in opposite (tTamman = tfusion /2) of V2 O5 (340 ◦ C), a very small
directions, these shifts could express the interaction amount of V2 O5 would migrate at low reaction tem-
between the phases. Apparently, when SmVO4 con- peratures (350–400 ◦ C). Although, small, this amount
tent increases, a stronger interaction with vanadium is would be enough to cause a SmVO4 surface contami-
observed. The shift of the last peak (V4+ to V3+ ) to nation. The SmVO4 artificial contamination with vana-
lower temperatures could be due to some way of ac- dium (work in progress) has demonstrated by Raman
tivation of reducing hydrogen species. It is probable and TPR that when the vanadium surface amount is
that at high temperatures, a spillover hydrogen Hso small, it is present in the form of adsorbed surface
(proposed by Delmon) capable of migrating and facil- VOx species. When the loading of vanadium increases,
itating the reduction to V3+ would become active. the formation of V2 O5 crystals is favored. This is
When the vanadium is in close contact with the what would occur on the mechanical mixtures when
support as adsorbed surface VOx species in the the temperature of catalytic test is increased. As the
272 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273

reaction temperature increases, V2 O5 migration would Pasteur of Strasbourg is gratefully acknowledged. Au-
be high enough to cover to a large extent the SmVO4 thors also thank Dr. L. Hilaire for his help in XPS
surface in the form of large conglomerates of VOx measurements.
species and also to form V2 O5 crystallites. The re-
sults obtained by EPR before and after the test show a
decrease of V4+ species concentration enhancing the References
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