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-

The transformation of alkanes into useful interme-
diates is currently the object of intense investigations
in the field of catalysis. It is possible to obtain alkenes
from short chain alkanes by catalytic dehydrogenation.
However, the dehydrogenation of the alkane to give
the corresponding alkenes and H2 is a strongly en-
dothermic process which has to be carried out at tem-
peratures >600 ◦ C. At these high reaction temperatures
needed, other unwanted reactions leading to coke also
occur, and the catalyst needs frequent regeneration.
∗ Corresponding author. Fax: +54-2652-426711.
E-mail address: lcadus@unsl.edu.ar (L.E. Cadus).
tion would be the oxidative dehydrogenation. In this
process the hydrogen abstracted is oxidized and the
absolute heat of reaction is sensibly reduced. There-
fore, the process becomes significant at a much lower
reaction temperature.
The vanadia-based systems are active and selective
in various types of hydrocarbon oxidation reactions
comprising: (a) oxidative dehydrogenation of alka-
nes and alkenes and (b) reactions with formation of
the oxygenated products. The V-Mg-O catalysts have
been proposed to be active and relatively selective
in the oxidative dehydrogenation of propane and bu-
tane [1–11]. Three Mg vanadate phases were found to
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 co-workers attributed the active phase to mag-
nesium orthovanadate (Mg3 V2 O8 ) [2], but Volta and
co-workers suggested that magnesium pyrovanadate
(␣-Mg2 V2 O7 ) was the active phase and Mg3 V2 O8
was responsible for total oxidation [3]. Further, Gao
et al. prepared three pure phases of magnesium vana-
dates and confirmed that in the oxydehydrogenation
of propane, ␣-Mg2 V2 O7 was the most selective and
MgV2 O6 was the worst [6]. It must be noted from
those studies [2,3] that in their V-Mg-O working cat-
alysts, at least two phases have been identified simul-
taneously. Thus, it is reasonable to suspect that the
overall catalytic behavior should not be attributed to
just one phase. In fact, Gao et al. also found that the
coexistence of ␣-Mg2 V2 O7 or MgO with Mg3 V2 O8
in intimate contact could promote the selectivity to
propene of Mg3 V2 O8 [11].
In many other cases, it has been found that the
catalytic properties of the multiphasic catalysts are
remarkably different from those of the individual
constituents. Activity and/or selectivity enhancement,
which has been observed when two phases are present,
is of wide interest [11–14]. On the other hand, few
examples, have been reported about the catalysts
preparation for oxidative dehydrogenation of propane
by replacing magnesium with rare earth [15–19], al-
though some rare earth orthovanadates have shown
to be almost as selective as the magnesium vanadates
for the oxidation of butane [20]. In this paper, the
preparation and the physicochemical characteriza-
tion of the mechanical mixtures containing different
amounts of SmVO4 and V2 O5 is reported. In addi-
tion, a synergy cooperation between the two phases
in the oxidative dehydrogenation of propane at low
reaction temperature is shown.
2. Experimental
2.1. Catalyst preparation
2.1.1. Pure oxides: vanadium pentoxide and
samarium orthovanadate
V2 O5 was prepared by calcination in air of NH4 VO3
(Mallinckrodt) at 450 ◦ C for 4 h.
SmVO4 was prepared by the citrate method [21].
Sm(NO3 )3 ·6H2 O (Fluka), NH4 VO3 (Mallinckrodt)
and citric acid (Mallinckrodt) were used as reagents.
An aqueous solution of citric acid with a 10% ex-
cess over the number of ionic equivalents of cations
(three ions per molecule of citric acid) was pre-
pared. The aqueous solution of Sm(NO3 )3 ·6H2 O
was added to that of citric acid and it was agitated
for 30 min. Then the aqueous ammoniacal solution
of NH4 VO3 was added and agitated for 30 min.
The amounts of Sm(NO3 )3 ·6H2 O and NH4 VO3
used, corresponded to the molar ratio Sm:V = 1:1.
The resulting solution was concentrated by evap-
orating water slowly in vacuum in a rotavapor at
70 ◦ C until a gel was obtained. This gel was dried
in a vacuum oven at 70 ◦ C overnight. The result-
ing solid was ground and then heated slowly up
to 400 ◦ C in order to decompose the organic pre-
cursor, and then it was calcined at 600 ◦ C for
3 h.
2.1.2. V2 O5 –SmVO4 mechanical mixtures
Mechanical mixtures of separately prepared V2 O5
and SmVO4 were obtained with different SmVO4 con-
tents. The corresponding powders were dispersed and
mixed in n-pentane with the help of an ultrasonic de-
vice and were subsequently evaporated under reduced
pressure at room temperature to remove the solvent.
The solid was dried at 100 ◦ C during 12 h. No further
calcination was carried out in the resulting mechanical
mixtures. The samples with 8.5 and 31.5 wt.% SmVO4
are referred as mmSmV8.5 and mmSmV31.5, respec-
tively.
2.2. Catalyst characterization
2.2.1. Specific surface area measurements (BET)
Specific surface areas (SSA, m2 /g) were determined
from nitrogen adsorption isotherms at 77 K by the
BET method. Samples were previously outgassed in
vacuum at 200 ◦ C. A Micromeritics Accusorb 2100E
apparatus was used.
2.2.2. X-ray diffraction (XRD)
XRD patterns were obtained by using a Rigaku
diffractometer operated at 30 kV and 25 mA by
employing Ni-filtered Cu K␣ radiation (λ =
0.15418 nm). The crystalline phases were identi-
fied by reference to the powder diffraction data
(JCPDS-ICDD).
 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273
2.2.3. Temperature programmed reduction (TPR)
The temperature programmed reduction was carried
out in a quartz U-type tubular reactor using a TCD as
a detector. A 20 mg sample without any previous treat-
ment was used. The reducing gas was a mixture of
4 vol.% H2 /Ar at a total flow rate of 50 ml/min. Tem-
perature was increased at a rate of 15 ◦ C/min, from
room temperature to 900 ◦ C. The temperature was kept
constant at 900 ◦ C until the signal of hydrogen con-
sumption returned to the initial values.
2.2.4. X-ray photoelectron spectroscopy (XPS)
An VG ESCA III equipment was used. The radi-
ation K␣ of Mg was its non monochromatic X-ray
source. The source was operated at 11 kV and 20 mA.
A 20 eV pass energy was used. Spectra were registered
after purging the samples at room temperature in vac-
uum (10−9 Torr) overnight. The fine-powder samples
were prepared in the form of pellets and were pressed
at 25 kN/cm2 . The charging effect was corrected with
reference to C 1s binding energy at 284.8 eV. Spec-
tra were deconvoluted with an appropriate software.
Surface atomic ratios were estimated by the corre-
sponding peak area ratios using the effective ioniza-
tion cross-section values tabulated by Scofield [22]
and also making corrections based on the number of
scans and the characteristic kinetic energies of the an-
alyzed elements.
2.2.5. Electron paramagnetic resonance (EPR)
Spectra were obtained using a Bruker ESP 300
Spectrometer operated at X-band at a temperature of
120 K. Resulting spectra were treated with a specially
designed software.
2.3. Catalytic test
The catalysts (1 g, 0.5–0.8 mm particle diameter)
were tested in a fixed bed, quartz tubular reactor oper-
ated at atmospheric pressure. The temperature, mea-
sured with a coaxial thermocouple, varied between
350 and 500 ◦ C. The feed was a mixture of 4 vol.%
propane, 4 vol.% oxygen, and balanced with helium.
The flow rate was 100 ml/min at room temperature.
The reactants and reaction products were alternately
analyzed on-line by a Shimadzu GC9A gas chromato-
graph equipped with a thermal conductivity detector.
A Porapaq Q (80–100 mesh) column for separating
265
hydrocarbons and CO2 and a Carbosphere column for
carbon monoxide, methane and oxygen were used. The
homogeneous contribution was tested in the empty re-
actor. These runs showed no activity <550 ◦ C. The
results were very similar with and without the use of
quartz particles.
The conversion and selectivity for products were
defined as follows:
Selectivity for product i, (Si ) is given by
y i ni
Si =

yi ni
Conversion of propane, XC3 H8 , is given by


yi ni
XC3 H8 =

(yC3 H8 nC3 H8 + yi ni )
where yi and yC3 H8 are the mole fractions of product
i and propane, respectively; and ni and nC3 H8 are the
number of carbon atoms in each molecule of prod-
uct i and propane, respectively. All terms were to be
evaluated for the exit stream. The carbon balance was
found to be ±4%.
3. Results
3.1. Specific surface area (BET)
In Table 1, the specific surface areas (SSA) ob-
tained with pure phases and mechanical mixtures are
shown. The areas of the mechanical mixtures are in
good agreement with the expected theoretical values
defined as:
(wt.% V2 O5 ) · SSAV2 O5
+(wt.% SmVO4 ) · SSASmVO4
SSAtheoretical =
100
After the catalytic test, V2 O5 specific surface area de-
creases strongly (41%), the surface areas of mechani-
cal mixtures decrease about 25% and that of SmVO4 ,
practically does not change.
3.2. X-ray diffraction (XRD)
The XRD results of mechanical mixtures before the
catalytic test are shown in Fig. 1. They indicate the
presence of V2 O5 and SmVO4 and there is no evidence
of new phases. The intensities of signals correspond-
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-

Fig. 3. TPR profiles of the catalysts.
As an example, Fig. 2 shows the XRD patterns of the
mmSmV31.5 catalyst both fresh and used. After the
catalytic test, the same phases are present, although a
relative decrease of V2 O5 signal intensity in compar-
ison to that of SmVO4 is observed.
3.3. Temperature programmed reduction (TPR)
face atomic ratio of mmSmV31.5 catalyst increases
from approximately 6 to 11.6 by effect of the catalytic
test. To discriminate between the effect of temperature
and of reaction atmosphere, the mmSmV31.5 sample
calcined at 550 ◦ C without undergoing catalytic test
conditions was analyzed. The results indicate that the
surface enrichment in vanadium observed in the sam-
ple after the catalytic test occurs mainly under reaction
conditions.
No shift in values of V 2p3/2 binding energies by
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
value equal to that of V2 O5 . Signal intensity of me-
chanical mixtures decreases as SmVO4 proportion in
the sample increases. When spectra of fresh samples
are compared with those of the samples after the cat-
alytic test, a decrease of signal intensity is observed
(Fig. 4).
Figs. 5–7 show the results of catalytic activity. The
major products were propene, CO and CO2 . Other
oxygenated products were not found. Curves of se-
lectivity to C3 H6 as a function of C3 H8 conversion of
mechanical mixtures (Fig. 5) present the same decreas-
ing form as that of V2 O5 . Conversely, SmVO4 curve
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,
the consecutive combustion of propene on SmVO4 is
slower than that on V2 O5 . Fig. 6 shows propane con-
version as a function of reaction temperature. A syn-
ergy effect on the mechanical mixtures can be inferred.
Taking in account the yield to propene (Fig. 7), this
synergy effect is observed at low reaction tempera-
tures (350 and 400 ◦ C) but it disappears at 450 ◦ C.
At higher reaction temperatures (500 ◦ C) the yield to
propene of mechanical mixtures is lower than that of
pure phases. The mechanical mixtures tested at 500 ◦ C
were re-evaluated. An important decrease in the yield
to propene at low reaction temperatures (350–400 ◦ C)
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
Most of active and selective catalytic systems in re-
actions of propane oxydehydrogenation are multipha-
sic. In general, these phases are interdispersed and the
presence of arrangements within the detection range of
the used characterization techniques is not evident. In
a previous work [23], the evolution of Sm-V-O system
by a solid state reaction was studied. Artificially, V2 O5
was contaminated with different amounts of samarium
by using the technique of impregnation. The detected
phases corresponded to SmVO4 and V2 O5 . The cat-
alytic performance of the impregnated catalysts did
not be different from that of pure V2 O5 due to that
the surface becomes enrichment in vanadium. Many
works reported in the literature mention synergy ef-
fects between the phases present in a catalyst [11–14].
However, there is no agreement on whether such syn-
ergy effect is the result of cooperation between the
phases or it is simply due to the formation of arrange-
ments with a catalytic behavior different from that
of pure phases. The catalytic evaluation of mechani-
cal mixtures of V2 O5 and SmVO4 presents interesting
points to be enhanced. In fact, the catalytic perfor-
mance of mechanical mixtures is not the simple con-
tribution of the phases which constitute the mixtures.
While V2 O5 exhibits a high selectivity to propene at
low conversions of propane and this selectivity de-
creases markedly as the conversion increases, SmVO4
presents a relatively good selectivity to low conversion
levels which is maintained as the conversion increases
(Fig. 5). This simple observation leads to the conclu-
sion that when the pure phases (V2 O5 or SmVO4 ) are
used, the side reactions considered in the ODH re-
action mechanism [24] proceed at different reaction
rates. In both mechanical mixtures, there is a similar
behavior to that observed on V2 O5 . This would indi-
cate that, as with V2 O5 , the consecutive combustion
of propene occurs fast.
The first significant observation about catalytic
performance is that, at reaction temperatures of
350 and 400 ◦ C, the yield to propene obtained with
V2 O5 –SmVO4 mechanical mixtures is higher than
that expected by the contribution of each individual
phase while at 500 ◦ C, it is lower. The fact that the
synergy effect disappears as the reaction temperature
increases is not consistent with the other researchers’
observations [13].
During the preparation step of mechanical mixtures
the possible contamination between the constituent
phases was avoided. The original phases of mechanical
mixtures were prepared separately. During the mixing,
the temperature was never higher than 70 ◦ C and the
solvent used was a non-polar compound. According to
these considerations, it seems reasonable to expect that
mmSmV fresh catalysts result to be constituted by the
two well-defined original phases without interaction or
contamination between them. The characterization of
fresh mechanical mixtures suggests that the nature of
the constituted phases is not affected during the prepa-
ration step, this corroborates the previous assumption.
In fact, the results of BET specific surface area of fresh
mechanical mixtures are in good agreement with the
expected theoretical values. This would indicate that
the specific surface area of mixtures is the result of the
contribution of each one of the phases. A solid state
reaction, improbable at synthesis temperature, would
cause modifications in the specific surface area. The
diffractograms of mechanical mixtures show the char-
acteristic lines of the two original phases, V2 O5 and
SmVO4 , with intensities proportional to the composi-
tion. No new phase was detected. Numerous reported
studies [11,13,14] on mechanical mixtures prepared in
similar conditions have not detected either new phases
or contamination between the original phases.
The reaction temperature is relatively high and the
XPS results proved that the reacting atmosphere con-
tributes to the redefinition of the surface. In order to
understand the behavior of this system, it is very im-
portant to compare the characterization results before
and after the catalytic test. In fact, the XRD results
of used samples compared with fresh ones indicate a
relative increase in the intensity of lines correspond-
ing to SmVO4 with respect to those of V2 O5 (Fig. 2).
This gives an insight that there is a modification of the
system during the reaction, although the appearance
of new phases was not observed. It could be assumed
that SmVO4 crystallinity increases and, therefore, its
signal becomes more intense. However, this hypoth-
esis is difficult to support considering that SmVO4
was calcined at 600 ◦ C for 3 h during its preparation
and that the reaction temperature was not higher than
500 ◦ C. Other possible explanation of the phenomenon
observed by XRD could be that the V2 O5 phase be-
comes more amorphous and, thus, its signal inten-
sity decreases. The measurements of specific surface
 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273
area show interesting hints to determine what has oc-
curred. BET specific surface area of V2 O5 decreases
strongly after the catalytic test while that of SmVO4
practically does not vary. It is also important to note
that after the catalytic test, the specific surface area
of the mmSmV31.5 mixture is quite lower than the
expected theoretical specific surface area, i.e. it de-
creases more than what was foreseen by effect of the
reaction. In mmSmV31.5 sample, an important part
of the surface area is supplied by the SmVO4 phase.
This effect is not so evident in mmSmV8.5 catalyst
in which the surface area supplied by SmVO4 is less
important.
These observations indicate that the process by
which V2 O5 crystallinity decreases gives rise to a
deep reformulation of the catalyst capable of affecting
its textural characteristics.
Assuming that no technique can provide by itself the
information necessary for elucidating this situation, a
combination of TPR, XRD and XPS has been used.
The TPR profiles measured for the mechanical mix-
tures showed that the reduction curves result from
the contribution of the two original phases. However,
some differences are not negligible. As SmVO4 con-
tent in the mechanical mixtures increases, the Tmax of
the first two reduction stages shifts to higher temper-
atures. It would indicate that the interaction between
the phases makes the reduction of these stages more
difficult, while the reduction of the last stage of V2 O5
is facilitated by the presence of SmVO4 . By XRD it
was determined that the first reduction stage of V2 O5
corresponds to V5+ transformation into a mixture of
V5+ to V4+ and the second stage, into the complete
reduction to V4+ . At the end of the reduction process
all the vanadium is V3+ [23]. As SmVO4 content in
the mechanical mixtures increases, a greater shift of
the reduction peaks is observed. Although in opposite
directions, these shifts could express the interaction
between the phases. Apparently, when SmVO4 con-
tent increases, a stronger interaction with vanadium is
observed. The shift of the last peak (V4+ to V3+ ) to
lower temperatures could be due to some way of ac-
tivation of reducing hydrogen species. It is probable
that at high temperatures, a spillover hydrogen Hso
(proposed by Delmon) capable of migrating and facil-
itating the reduction to V3+ would become active.
When the vanadium is in close contact with the
support as adsorbed surface VOx species in the
271
V2 O5 /TiO2 catalysts, a TPR peak at Tmax ≈ 500 ◦ C
is observed [25].
Although new TPR peaks which would explain the
decrease of V2 O5 crystallinity with the increase of
SmVO4 content are not observed, a new surface ar-
rangement can be assumed from the interaction be-
tween phases. This new surface arrangement should
facilitate the contact between the phases in order to
that the mentioned interaction occurs. The techniques
of massive characterization have given hints of the
changes which would explain the catalytic behavior.
In order to know what the supposed changes of the
surface arrangement are like, surface techniques were
used. Measurements of mmSmV31.5 sample surface
composition by XPS before and after the catalytic test
were carried out. It was found that V 2p3/2 /Sm 4d
surface atomic ratio changes from approximately 6 in
the fresh sample to 11.6 in the used one. This result
clearly indicates that there is a vanadium surface en-
richment during the reaction. As it has been reported
in the literature [26], V2 O5 has the capacity to migrate
on the surface of other solids enveloping them with a
thin overlayer. However, it is in doubt whether the ef-
fect is due to the temperature or to reaction atmosphere
conditions. To discriminate between the effect of tem-
perature and the reaction atmosphere, mmSmV31.5
mechanical mixture was analyzed by XPS after cal-
cinating it at 550 ◦ C. The results indicate that the re-
action test plays a key role in the reformulation of
the catalytic surface. Taking in account that water is
a reaction product in the oxidative dehydrogenation
of alkanes, this observation is in agreement with pub-
lished studies on the influence of the moisture in the
migration of vanadium oxide and molybdenum oxide
[27–29].
Taking into consideration the Tamman temperature
(tTamman = tfusion /2) of V2 O5 (340 ◦ C), a very small
amount of V2 O5 would migrate at low reaction tem-
peratures (350–400 ◦ C). Although, small, this amount
would be enough to cause a SmVO4 surface contami-
nation. The SmVO4 artificial contamination with vana-
dium (work in progress) has demonstrated by Raman
and TPR that when the vanadium surface amount is
small, it is present in the form of adsorbed surface
VOx species. When the loading of vanadium increases,
the formation of V2 O5 crystals is favored. This is
what would occur on the mechanical mixtures when
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
be high enough to cover to a large extent the SmVO4
surface in the form of large conglomerates of VOx
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
influence of the reaction test operation conditions.
That decrease indicates there is an equilibrium
that favors the presence of reduced species (the gen-
eral balance of the system suggests that, in presence
of oxygen, the system remains reduced [30]). This
equilibrium would be controlled by the reaction test.
Perhaps, under different operation conditions, equilib-
rium would be reached at other point of concentration
of V4+ spins.
Thus, the description of the surface architecture ex-
plains the catalytic behavior of mechanical mixtures of
V2 O5 and SmVO4 . The apparent synergy observed in
the yield to propene at low reaction temperatures could
be explained by the effect of contamination of SmVO4
surface with non-crystalline vanadium species of VOx
type. The disappearance of the synergy at high temper-
atures would be the result of the generation of V2 O5
crystals due to a great amount of vanadium which has
migrated to SmVO4 surface. The surface transforma-
tion of the mechanical mixtures under reaction condi-
tions is irreversible. This was corroborated repeating
the catalytic test on the samples previously tested.
The changes caused by the reaction test would oc-
cur in a short period of time at the beginning of the
operation time. The ‘apparent’ synergy is unfortu-
nately as unstable as solid system since while vana-
dium is in excess, it will tend to cover the SmVO4
surface. This migration occurs even under conditions
of contact between the phases as disadvantageous as
those provided by mechanical mixtures. According to
this system description, whenever vanadium exceeds
the necessary amount for SmVO4 stoichiometry, the
system will show a catalytic performance similar
to that of V2 O5 . Very small amounts of vanadium
strongly interacted with SmVO4 incapable of form-
ing V2 O5 crystals would be useful for improving the
catalytic performance.
Acknowledgements
The financial support of CONICET, Universidad
Nacional de San Luis and ECPM, Université Louis
Pasteur of Strasbourg is gratefully acknowledged. Au-
thors also thank Dr. L. Hilaire for his help in XPS
measurements.
References
[1] M. Chaar, D. Patel, M. Kung, H.H. Kung, J. Catal. 105 (1987)
483.
[2] M.A. Chaar, D. Patel, H.H. Kung, J. Catal. 109 (1988)
463.
[3] D. Siew Hew Sam, V. Soenen, J.C. Volta, J. Catal. 123 (1990)
417.
[4] A. Guerrero-Ruiz, I. Rodriguez-Ramos, J.L.G. Fierro, V.
Soenen, J.M. Hermann, J.C. Volta, Catal. Stud. Surf. Sci.
Catal. 72 (1992) 203.
[5] A. Corma, J.M. López Nieto, N. Paredes, A. Dejoz, I.
Vazquez, in: V. Cortés Corberán, S. Vic Bellón (Eds.),
Proceedings of the II World Congress and IV European
Workshop Meeting on New Developments in Selective
Oxidation, Benalmádena (Spain), 1993, p. B-4.
[6] X. Gao, P. Ruiz, Q. Xin, X. Guo, B. Delmon, Catal. Lett. 23
(1994) 321.
[7] H.H. Kung, M.C. Kung, Appl. Catal. A 157 (1997)
105.
[8] A. Pantazidis, A. Burrows, C.J. Kiely, C. Mirodatos, J. Catal.
177 (1998) 325.
[9] A. Burrows, C.J. Kiely, J. Perregaard, P.E. Hojlund-Nielsen,
G. Vorbeck, J.J. Calvino, C. López-Cartes, Catal. Lett. 57
(1999) 121.
[10] A. Corma, J.M. López Nieto, N. Paredes, J. Catal. 144 (1993)
425.
[11] X. Gao, P. Ruiz, Q. Xin, X. Guo, B. Delmon, J. Catal. 148
(1994) 56.
[12] U.S. Ozkan, M.R. Smith, S.A. Driscoll, Stud. Surf. Sci. Catal.
72 (1992) 363.
[13] L.E. Cadús, M.F. Gómez, M.C. Abello, Catal. Lett. 43 (1997)
229.
[14] N.G. Valente, L.E. Cadus, O.F. Gorriz, L.A. Arrúa, J.B.
Rivarola, Appl. Catal. A 153 (1997) 119.
[15] A. Corma, J.M. Lopez-Nieto, N. Paredes, M. Perez, Y.
Shen, H. Cao, S.L. Suib, Stud. Surf. Sci. Catal. 72 (1992)
213.
[16] J. Castiglioni, P. Poix, R. Kieffer, Stud. Surf. Sci. Catal. 75
(1993) 2309.
[17] B. Zhaorigetu, R. Kieffer, J.P. Hindermann, Stud. Surf. Sci.
Catal. 101 (1996) 1049.
[18] C.T. Au, W.D. Zhang, H.L. Wan, Catal. Lett. 37 (1996)
241.
[19] Z.M. Fang, Q. Hong, Z.H. Zhou, S.J. Dai, W. Zheng, H.L.
Wan, Catal. Lett. 61 (1999) 39.
[20] D. Patel, P.J. Andersen, H.H. Kung, J. Catal. 125 (1990)
132.
[21] P. Courty, H. Ajot, C. Marcilly, B. Delmon, Powder Tehnol.
7 (1973) 21.
[22] J.H. Scofield, J. Electron. Spectrosc. Relat. Phenom. 8 (1976)
129.
 B.P. Barbero, L.E. Cadus / Applied Catalysis A: General 237 (2002) 263–273 273

[23] B. Barbero, L.E. Cadús, Appl. Catal. A 234 (2002)
247.
[24] T. Blasco, J.M. López Nieto, Appl. Catal. A 157 (1997)
117.
[25] R.A. Koeppel et al., J.C. Vedrine (Ed.), Catal. Today 20
(1994) 45.
[26] J. Haber, T. Machej, T. Czeppe, Surf. Sci. 151 (1985) 301.
[27] G. Hausinger, H. Schemlz, H. Knözinger, Appl. Catal. 39
(1988) 267.
[28] G. Centi, D. Pinelli, F. Trifiro, Stud. Surf. Sci. Catal. 67
(1990) 1.
[29] M. del Arco, S.R. Carrazán, V. Rives, F.J. Gil-Llambı́as, P.
Malet, J. Catal. 141 (1993) 48.
[30] B. Delmon, Appl. Catal. A 113 (1994) 121.