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Along with the bands of V20S and zirconia, a strong Raman band at 777cm-
1
is apparent in the spectra of the VZr-6.0 and VZr-9.4 samples. The presence
of this band together with an observed broadeningof the band at 995cm-1 and
the appearance of shoulders at 1024 and 953 cm"' clearly points to the fact
that ZrV207 has formed. Only some weak bands are present in the spectrum of
the VZr-19.4 sample, and they all are from V
2
0
S
'
The Raman technique when applied to supported vanadia catalysts has been
found sensitive to surface structure and coverage of the support [47]. There-
fore, for quantification, the bands at 145 and 778 cm-1 were selected as char-
acteristic for V
2
0
S
and ZrV
2
0
7
, respectively, while the two bands at 615 and
638 em-1 were chosen for the support. For the supported catalysts, the inte-
grated intensities of these bands relative to the intensities of the same bands
in the pure oxides were calculated and are plotted in Fig. 2 as a function of the
vanadium oxide content. A strong decrease in intensity of the zirconia bands
is observed with increase in loading up to a theoretical monolayer. At higher
58
1
0
.
1
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72
i lx
h lx
1200 1000 800 600 400 200
Wavenumber (em-
1
)
Fig. 1. Raman spectra ofBupported catalysts and of reference samples. (a) Zr02; (b) VZr-O.6; (c)
VZr-1.2; (d) VZr-2.6; (e) VZr-6.0; (f) VZr-9.4; (g) VZr-19.4; (h) ZrV
207
; and (i) V
205
Factors
by which the Raman intensity has been expanded are inserted.
loadings, this decrease is more modest. Both V205 and ZrV207 are present at
intermediate loadings. However, at the highest vanadia loading investigated,
only V205 bands were present but with low intensity. The variation of the
difference in balance to 100%, which is also plotted in the figure, indicates at
low loading a predominance at the surface for monolayer species, giving Ra-
man bands in the 1030-820 cm-1 region. At higher loading, beside some V205
and ZrV207 the surface seems covered with an amorphous phase.
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72 59
100
80
iii
c
III
60
c
'" E
'"
40
II:
III
20
a;
II:
o
o 10 20 30 40
Vanadium OXide Content (wt.o V205)
Fig. 2. Relative intensity (compared with pure phases) of some Raman bands characteristic for
Zr02. ZrV
207
and V
205
plotted as a function of the vanadium oxide content of the supported
catalysts. (0) Zr02 bands at 638 and 615 cm-1 integrated within 672-584 em-1; (.) V205band
at 145cm- 1 integratedwithin 162-113 em-1; and (D) ZrV207band at 778cm-1 integratedwithin
724-845 cm"". (e) Difference in balance to 100%.
Infrared spectroscopy
DRIFT spectra of supported catalysts, support, V
2
0
S
and ZrV
2
0
7
are given
in Fig. 3. Two vibrational regions are shown, the 1200-750 cm-
I
region and
the region around 2000 cm-1. The latter region gives information about the
overtones of vanadyl stretching fundamentals around 1000cm-1.
The zirconia support has no band in the two regions. V20S has a strong band
at 1020 cm" ' and a weak band at 982 cm-
I
that are from the symmetric and
asymmetric v(V=O) vibration, respectively, while the band at 845 em>' is a
V-0-Vstretching mode [46] . The overtones of the vanadyl fundamentals are
at 2020 and 1971cm-
1
ZrV
2
0
7
has a broad band centred at 859 cm-
I
Also, a
poorly resolvedbut strong band is at 972 cm-1 surrounded by two weaker bands
at 1023 and 931 cm-
1
Two more bands appear at 1115 and 1064 cm-I, and
they were present neither in the corresponding Raman spectrum, cf. Fig. 1, nor
in any catalyst DRIFT spectrum. It was shown that the appearance of the
latter two bands was related to the particle size of ZrV207' since further grind-
ing of the pure ZrV207 sample down to a particle size around 2/-lm caused 70%
reduction of their intensities, while the intensities of the other bands slightly
increased. At higher wavenumbers, ZrV
2
0
7
has a band at 1979 cm-
1
and a
shoulder is around 1940cm-
1
The spectrum of ZrV
2
0
7
in Fig. 3 was recorded
after grinding.
Considering the spectra of the supported catalysts, VZr-0.6 gives a band at
993 cm" ', and for VZr-1.2 an additional shoulder around 1020cm" ' is appar-
ent. The corresponding first overtones are around 2030 and 1980 cm-1. Pos-
sibly, these bands are from monolayer species interacting with the zirconia.
60
M. Sanati et al. / Appl. Gata/. A 106 (1993) 51-72
I'
I \
/q
20L
h
J ~
"
e (\
.2
/ ~
u
c
"
~
J
d
~
c
~
b
~
a
10.02
lOx
2100 2000 1900
i I \ ~
0\;
h
~
,
g
I ~
~
f
,
/
e?
~
..:
3x
c
,
/
J
~ ~ /
.
a
,
110
4x /
I
, , ,
1100 1000 900 800
WAVENUMBER (cm'
1
)
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72 61
Beside the band at 993 cm-1, two bands at 1020and 845 cm-1 from crystalline
V205 are seen in the spectrum of VZr-2.6. At higher vanadia loadings, both
crystalline V205 and ZrV207 are formed. The spectrum of VZr-6.0 has bands
from V205 at 1020 and 845 cm-1, and from ZrV207 a strong band at 982 cm-
1
and a weak broad band around 936 cm-1 are present. Formation of ZrV207 is
further supported considering the spectral features around 1980 cm-1. In the
spectrum of VZr-9.4, the bands from crystalline V205 are more dominant, but
the band at 982 cm-1 and the shoulder around 1920 cm-1 are from ZrV207'
For the VZr-19.4 sample the spectrum shows in both spectral regions strong
6
Par no. 2
10
27%U
73% 2r
6
Par. no. 1
91% U
U 9% Zr
u
BOX spo a lysis of
par teres
2r
Fig. 4. Secondary electron image of individual grains of the VZr-9.4 catalyst, overlaid with energy
dispersive X-ray maps of zirconiumand vanadium. Amarked difference in composition is obvious
from the spectra shown for two selected particles.
Fig. 3. DRIFT spectra of catalysts and reference compounds. Left: 2150-1850 cm" ': right: 1200-
750 cm" '. (a ) z-o; (b) VZr-0.6; (c) VZr-1.2; (d) VZr-2.6; (e) VZr-6.0; (f) VZr-9.4; (g) VZr-
19.4; (h) ZrV
2
0
7
; and (i ) V
2
0
6
Factors by which the KM-function has been expanded are inserted.
62 M. Sanatietal. I Appl. Catal.A 106(1993)51-72
bands from crystalline V
205
. However, also new bands at 1041 and 1002 cm"
have appeared. These bands were not apparent in the corresponding Raman
spectrum, in which only weak bands from V205 were seen (cf. Fig. 1). This
difference can be due to the Raman technique compared with DRIFT spec-
troscopy is more surface sensitive.
Scanning electron microscopy and energy dispersive X-ray analysis
EDX vanadium maps of the pure Zr02 support did not show any significant
differences from simultaneously recorded maps of background areas without
any characteristic peaks, using windows of the same width. Quantification of
point analyses of random Zr0
2
particles showed the noise level for vanadium
to correspond to less than 1 atom-%. No contaminants were present above that
level.
EDX analyses ofthe VZr-2.6 sample showed the vanadium to be evenly dis-
tributed. The vanadiumatompercentages, V/ (V+Zr) '100, ranged from 16to
34%, to be compared with the nominal value of 11.4%. Since the structures
rich in vanadia form at the surface of the support, the composition measured
will vary with particle size and surface area. The probed depth with 20 keV
primary electrons is approximately 1/lID in this type of material [48). In a few
cases, very high zirconium contents were observed, mostly for grains that were
very smooth in appearance. These probablywere large single crystals of zirconia.
Fig. 5. SEM images of (a) : particle no. 1, and (b) : particle no. 2 from Fig. 4 at higher magnifica -
tion. The vanadium rich particle has a coarser, polycrystalline appearance. The bright spot in (b)
marks the site for spot analysis.
M. Sanati et al. / Appl. Cata!. A 106 (1993) 51-72 63
Mapping of elements in the VZr-9.4 sample, on the other hand, showed a
clear segregation into vanadium- and zirconium-rich areas. Fig. 4 shows the
secondary electron image overlaid with the zirconium map (lighter grey), which
in turn is overlaid with the map of vanadium (white). EDX spectra of the two
different grains marked 1and 2 are inserted in the figure. Quantification showed
in some cases a vanadium content greatly exceeding that of ZrV
207
(67 at.-
%), indicating that these grains possibly were V205' Comparison of the ap-
pearance of grains rich in either zirconium or vanadium, showed the former to
have smooth and clean surfaces, whereas the latter were irregular and deco-
rated with smaller particles, see Fig. 5.
High-resolution electron microscopy
HREM images of the pure support showed the particles, which according to
SEM micrographs were in the 1 JCffi range, to consist of aggregates of a large
number of smaller zirconia particles in the range 30-50 nm. Fig. 6 shows the
50nm
Fig. 6. Transmission electron micrograph of pure zirconia support, showing a grain consisting of
smaller particles with diameters around 30-50 nm. The inset electron diffraction pattern shows
t he particles to be crystalline and with random orientation.
64 M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72
Fig. 7. High-resolution low-dose image of pure zirconia support. The crystal lattices of different
grains have different orientation, but partly sintered together. Note that there is no amorphous
overlayer on the crystal surfaces.
smaller particles to be crystalline and with random orientation, giving ring
patterns in electron diffraction mode (see inset). The graininess of the rings
indicates that the crystallites are at least 20 nm in diameter. Diffraction peaks
derived from line traces of rotated electron diffraction patterns showed good
agreement with experimental and literature X-ray powder patterns. At higher
magnification, Fig. 7, it becomes apparent that the particles to a large extent
are sintered together, making it increasingly difficult to distinguish discrete
particles.
Comparing images of the pure support with those of the VZr-2.6 and VZr-
9.4 samples showed only subtle changes in appearance after deposition of van-
adia. An image of the VZr-9.4 sample is displayed in Fig. 8, and it shows that
the zirconia particles are covered with an amorphous overlayer. This layer is
not due to growth of contamination in the microscope, which is clear compar-
ing with the image of the pure support in Fig. 7 (see also the Experimental
section) . Generally, the surfaces of the crystals showed increased roughness at
the outermost layers.
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72 65
Fig. 8. High-resolution micrograph of the VZr-9.4 catalyst, showing an amorphous surface struc-
ture that is not present on the pure support. The thickness ofthe overlayer (arrowed) is typically
1.6nm.
Activity measurements
The performance of the prepared samples in toluene oxidation is shown in
Fig. 9. Zirconia has low activity and is not selective for partial oxidation, only
for combustion to mainly carbon dioxide. For the vanadia loaded samples, both
total activity expressed per unit surface area and the activity for formation of
benzaldehyde increase with increase in vanadia content up to about eight the-
oretical vanadia layers. With further increase in vanadia content, both activ-
ities decrease. The selectivity for benzaldehyde formation is 7%over VZr-0.6,
and it is around 23%over the other supported samples. For the ZrV207 sample,
the selectivity for aldehyde formation is 15%, while it is much higher, 45% (out
of scale in Fig. 9), over crystalline V20S' The total reaction rates over ZrV207
and V
2
0
S
are lower than for VZr-6.0 and VZr-9.4. Over V
2
0
S
, the rate for al-
dehyde formation is close to the values for VZr-6.0and VZr-9.4, but over ZrV207
it is lower.
Fig. 10 shows the rate per unit surface area and the selectivity for formation
of benzonitrile as a function of vanadia loading. Under the conditions of am-
moxidation, the zirconia support has no activity for formation of benzonitrile
66
12
":"
c
10
E
E
8
"0
E
3- 6
Q)
iii
a:
4
c
2
U
2
'"
Q)
a:
0
0
M. Sanati et al. / Appl. Catol. A 106 (1993) 51-72
25
...
c
20
2
iii
E
0
"
15
u.
Q)
'0
>-
s:
10
Q)
'0
<t
5
.E
u
0
Q)
Qj
5 10 15 20
C/)
Vanadia Loading (No. of layers)
Fig. 9. Total reaction rate (0), rate for formation of benzaldehyde (0) and selectivity for alde-
hyde formation (b,,) plotted as a function of the vanadia loading. Filled and half-filled symbols
showdata for ZrV207and V205,respectively. The reaction temperature was 370C, and the partial
pressures of toluene and oxygen were 0.77 and 11.4 kPa, respectively. For V
2
0
5
, the selectivity for
formation of benzaldehyde was 45% (out of scale).
100
e
c
"
80
2
iii
E
0
60
u,
.S!
.,S
40
Z
.E
.-
.
20
U
Q)
Qj
0
C/)
20 o 5 10 15
Vanadia loading (No. of layers)
Fig; 10. Total reaction rate (0), rate for formation ofbenzonitrile (0) and selectivity for nitrile
formation (b,,) plotted as a function of the vanadia loading. Filled and half-filled symbols show
data for ZrV
2
0
7
and V
2
0
5
, respectively. The reaction temperature was 370C, and the partial
pressures of toluene, oxygen and ammonia were 0.77,11.4 and 2.85 kPa, respectively.
6
c 5
E
'"
'E 4
"0
1-3
Q)
iii
a: 2
c
o
<3 1
'"
Q)
a:
and low activity for carbon dioxide formation. It is seen that both the total
activity and the activity for nitrile formation with increase in vanadia content
pass through maxima at a vanadia loading corresponding to about eight van-
adia layers. The selectivity for nitrile formation increases rapidly with increase
in vanadia loading and attains a value of about 80% for one theoretical layer
and above, which is approximately equal to the values that were obtained for
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72 67
ZrV207and V20S. Both the total rate and the rate for benzonitrile formation
are lower for ZrV207and V20Sthan for most of the supported samples.
DISCUSSION
Dispersion and vanadia species in the monolayer region
Figs. 1 and 2 show a strong decrease with increase in vanadia loading of the
Raman intensity of the support bands. For the VZr-0.6 sample about 30% of
the intensity of the support bands remains, compared with the pure support,
and the corresponding values for samples with loadings of a theoretical mono-
layer and above are less than 5%. These data reveal the dispersion ofvanadia
on the zirconia to be high, a fact that is also supported by the EDX analysis of
the VZr-2.6 sample, showing the vanadium to be evenly distributed. Recently,
for supported vanadia catalysts, we found a correlation between the V/ (sup-
port metal) atom ratio determinedby X-rayphotoelectron spectroscopy (XPS)
andthe intensity of the Raman bands of the supports Ti0
2,
Zr02' Hf0
2,
Nb
20S'
and Ta20s [49], confirmingthat FT-Ramanspectroscopy is a surface sensitive
technique. In the same work [49], for a monoclinic zirconia with low surface
area (4.3 m
2
/ g), we observed almost no further increase in the V/Zr atomratio
determined by XPS when the vanadia loading exceeded half a theoretical
monolayer, indicating a surface coverage with vanadia of about 50%. For the
same samples, the Raman intensity of the support bands compared to those of
the pure support was around 35%. Thus, the corresponding value for the pres-
ent samples 5%) is considerably less and indicates for these almost com-
plete coverage.
The Raman and infrared spectra in Figs. 1 and 3 for low vanadia loading
(VZr-0.6, VZr-1.2 and VZr-2.6) show several bands in the 820-1030 cm-
1
re-
gion that can be attributed dispersed vanadia species. In previous investiga-
tions have bands in the same spectral region been reported for vanadia on
zirconia at ambient conditions, and they have been assigned to different types
of vanadyl and vanadate structures [32,40,50-52]. In viewof the assignments
given by Deo and Wachs [51] for vanadia on various supports and which were
made considering both Raman and SlVNMR data, the Raman bands for VZr-
0.6 at 821 and 880 cm-
1
are assigned to orthovanadate (V0
4
) and pyrovana-
date (V207) species, respectively. The Raman band at 987 em-1 and the cor-
responding infrared bands at 993 cm-
1
(fundamental) and 1980 cm:' (first
overtone) are assigned to octahedrally coordinated vanadium oxide species in
a decavanadate-like (V
lO02S)
environment. The Raman and infrared bands
around 1020-1027 cm-
1
for VZr-1.2 and VZr-2.6, according to Deo and Wachs
[52] are from a dehydrated vanadate species possessing one terminal V=O
bond and three bridging V-O-support bonds. In a study of vanadia on Ti0
2,
Cristiani et a1. [11] assigned Raman and infrared bands at ca. 990 and 1035
68
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72
cm-1 to a mono-oxo species in hydrated and dehydrated form, respectively.
However, considering the high coverage of vanadia on zr0
2
that was obtained
in the present investigation, the band around 990 cm-1 more likely is from a
bidimensional polyvanadate structure of decavanadate type. This conclusion
is supported by calculations [53], showing that complete coverage with mon-
omeric species does not correspond to more than 30% of that expected for a
complete bidimensional polyvanadate layer. In our previous report on vanadia
supported on a zirconia with a low surface area [49], Raman and infrared
bands were both at ca. 1015 em-1. This might be due to another distribution
of Zr02 surface planes, a proposal that can explain the low dispersion of van-
adia on those samples.
Vanadia structures at high loading
At vanadia loadings above the theoretical monolayer region, the XRD (Ta-
ble 2), Raman (Fig. 1) and infrared (Fig. 3) analyses show formation of crys-
talline V205 and ZrV207' According to Fig. 2, the intensities of the Raman
bands of crystalline V205 and ZrV207 in the supported samples are low and do
not balance the corresponding decrease of the support bands. This observation
points to formation of at least one additional structure at high vanadia loading.
High-resolution electron micrographs reveal this structure to be an amorphous
overlayer, see Fig. 8. The formation of amorphous vanadia agrees with the
Raman spectrum for the VZr-19.4 sample in Fig. 1, where no band except very
weak V205 bands is apparent at high magnification. Interestingly, in our pre-
vious microscopy investigation [15], amorphous vanadia was discovered to
form on the surfaces ofthe anatase and rutile forms of Ti0
2
as well.
Formation on supports of some crystalline V205 has frequently been ob-
served [9,15,49,51], especially at high vanadia loading. Concemingthe present
samples, additionally, formation of some crystalline ZrV207is evident for VZr-
6.0 and VZr-9.4. For low loadings, however, there is no indication of ZrV
207
formation, an observation that agrees with data presented in other works where
calcination in air has been performed in the 40D-500C range [40,45,49,51].
Roozeboom et a1. [45], however, observed formation of ZrV207 after calcina-
tion of impregnated samples at 600C, in agreement with the minimum tem-
perature required starting from a mechanical mixture of V205 and Zr02 [35].
The calcination temperature used in the present work, 500C, is lower. It is
also considerably lower than the 710C, that in the present work (see the Ex-
perimental section) was found to be required for preparing ZrV207 from pow-
ders of V
205
and Zr02' Obviously, the formation of ZrV
207
in the catalyst
samples must be due to intimate contact between vanadium and zirconia, re-
sulting from the impregnation with vanadium salt.
There is no univocal evidence for ZrV207 formation on VZr-19.4. Some XRD
lines might be from ZrV
207
(Table 2), but there are no reflections at ca. 3.9
M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72 69
and ca. 3.6A, which typically are intense for crystalline ZrV207 [42]. Further-
more, there are no ZrV207bands in the corresponding Raman spectrum (spec-
trum g, Fig. 1). Possibly, these observations can be explained by formation of
either some poorly crystalline ZrV207 or a new unidentified structure, being
responsible for the infrared bands observed at 1041 and 1002cm-
1
(spectrum
g, Fig. 3).
Catalytic performance
The data in Figs. 9 and 10 show that the Zr02 support has low activity in
toluene oxidation and ammoxidation, respectively, and is selective for com-
bustion. Upon deposition of vanadia on the Zr02 surface, both the total activity
and the selectivity for formation of partial oxidation products increase, show-
ing that vanadia species are active for the formations of benzaldehyde and
benzonitrile. According to the vibrational spectra for VZr-0.6 and VZr-1.2 in
Figs. 1 and 3, the two predominant vanadia species for loadings in the mono-
layer range are an octahedrally coordinated species of decavanadate type and
a tetrahedral mono-oxo species. Although it has been demonstrated that the
former species upon complete dehydration converts to the latter species [51,52],
most likely the octahedral vanadia structure is dominant under reaction con-
ditions since water is formed as a product. For both toluene oxidation and
ammoxidation the total rate for VZr-1.2 expressed per unit surface area of
catalyst is almost twice the rate for VZr-0.6, verifying the dispersion of vanadia
to be high in the whole range up to a theoretical monolayer. Thus, the role of
Zr02 is not limited to that of being a physical support for vanadia, a conclusion
that is supportedby the presented infrared, Raman and EDX results. That the
selectivity for aldehyde formation for VZr-0.6is considerably less than for VZr-
1.2, in spite of the fact that the latter sample is more active per unit surface
area, can be explained by further reaction of benzaldehyde to carbon oxides on
the uncovered support surface. A similar finding has been reported for both
toluene and o-xylene oxidation on vanadia/titania catalysts [54,55]. For tol-
uene ammoxidation the selectivity for nitrile formation is comparatively high
for both VZr-0.6 and VZr-1.2, showing, compared with benzaldehyde, a greater
stability of benzonitrile toward degradation on the bare Zr02 surface.
Assuming the zirconia surface to be almost completely covered at a loading
of one theoretical monolayer, an assumption that is supported by the Raman
data in Fig. 2 and the EDX measurements, allows the conclusion that the sur-
face of multilayer amorphous vanadia with a thickness of 4-8 layers (Fig. 8)
is the most active structure for both toluene oxidation and ammoxidation, see
Figs. 9 and 10. In this regard it is worth noting that also for butene oxidation,
a correlation between activity and the concentration of amorphous vanadia on
Zr02 has been reported [32]. In disagreement with an earlier conclusion [39],
no evidence from activity measurements or microscopy was obtained in the
70 M. Sanati et al. / Appl. Catal. A 106 (1993) 51-72
present work for an oriented growth of V205 on the zr0
2
surface, leading to a
preferential exposure of the (010) V205 surface.
The activity data show the total rate to be higher in oxidation than in am-
moxidation, while a higher rate and selectivity for partial oxidation are ob-
served in ammoxidation. These differences can be explained by considering a
previous analysis of the structure-activity relationships in oxidation of alkyl-
aromatics over metal oxides [56], according to which structurally undercoor-
dinated oxygen participates in degradation and combustion pathways. On
crystalline V205' the (010) plane that is active for o-xyleneoxidation to phthalic
anhydride [57] exposes exclusively oxygens that are highly coordinated [3,5].
The V
2
0
5
(100) and (001) planes, on the other hand, expose strongly under-
coordinated oxygens [3,5] and are active for combustion [57]. Due to the lay-
ered structure of V205 [41], the crystals are anisotropic exposing large (010)
faces and small (100) and (001) faces. Therefore it is not surprising that crys-
talline V
2
0
5
until now is one of the most selective (ca. 45%) catalysts known
for benzaldehyde formation from toluene [15,54]. The much lower selectivity
obtained for the zirconia supported vanadia samples, therefore, possibly is due
to the fact that they expose undercoordinated oxygen species. For the design
of a supported catalyst that is more selective for benzaldehyde formation, a
tuning of the support-active phase interactions is needed to have an optimum
distribution and character of adsorption centres and oxygen species. This can
possibly be achieved using a support with additives. So far titania seems most
promising as support for vanadia in this reaction [15]. The higher rate and
selectivity of vanadia on zirconia for benzonitrile formation in ammoxidation,
compared with those for benzaldehyde formation in oxidation, can be seen as
a consequence of competitive adsorption of oxygen and ammonia, resulting in
a decrease of the concentration of undercoordinated oxygen species active for
combustion [58]. The explanation is supported by the fact that the selectivity
for benzonitrile formation generally is high (ca. 80%) irrespective of support
[15] andwhether the vanadia structure is V205' ZrV207, of decavanadate-type,
or amorphous.
ACKNOWLEDGEMENT
Ms. C. Song is gratefully acknowledged for assisting with EDX measure-
ments. Financial support from the National Board for Industrial and Techni-
cal Development (NUTEK) and the Swedish Research Council for Engineer-
ing Sciences (TFR) is also acknowledged.
M. Sanati et al. / Appl. Catal: A 106 (J993) 51-72
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71
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