ISSN 19907931, Russian Journal of Physical Chemistry B, 2015, Vol. 9, No. 5, pp. 721–725. © Pleiades Publishing, Ltd., 2015.

Original Russian Text © A.A. Baraboshina, T.V. Sviridova, A.I. Kokorin, E.N. Degtyarev, E.I. Romashevskaya, D.V. Sviridov, 2015, published in Khimicheskaya Fizika, 2015, Vol. 34,
No. 9, pp. 44–48.

DYNAMICS OF PHASE PROCESSES

Molybdenum–Vanadium Mixed Oxides Synthesized

by the Hydrothermal Method
A. A. Baraboshinaa, T. V. Sviridovaa, A. I. Kokorinb, E. N. Degtyarevb,
E. I. Romashevskayac, and D. V. Sviridova
a
Belarusian State University, Minsk, Belarus
b
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
c
Pirogov Russian National Research Medical University, Moscow, Russia
email: kokorin@chph.ras.ru
Received April 1, 2015

Abstract—The effect of pressure (5–20 MPa) on the process of hydrothermal synthesis of a molybdenum–
vanadium mixed oxide from a molybdenum–vanadium mixed poly(oxyacid) is studied. It is shown that the
synthesis product is a solid solution of isomorphically substituted vanadium pentoxide with a pressureinde
pendent composition. With increasing pressure, the degree of crystallinity of the synthesized products
increases, concentration of isolated V(IV) ions decreases, habitus of the crystals changes from prismatic to
needlelike, and overall dispersity increases. This makes it possible to regard the pressure as a dispersing factor
for the synthesis of nanostructured molybdenum–vanadium oxides.

Keywords: mixed oxides, vanadium, molybdenum, hydrothermal synthesis, EPR, phase analysis by Xray dif
fraction, electron microscopy, infrared spectroscopy
DOI: 10.1134/S1990793115050036

INTRODUCTION EXPERIMENTAL
An upsurge of interest in recent years in methods The Mo : V Mixed oxides were synthesized by
for controlled synthesis of mixed molybdenum–vana hydrothermal method at different pressures (5, 10 and
dium oxides is largely motivated by their high catalytic 20 MPa) from a 0.2 mol/L aqueous solution of a
activity in the oxidation of organic compounds with molybdenum–vanadium acid (with a V : Mo molar
molecular oxygen, which opens the possibilities for ratio of 1 : 1) prepared by ion exchange. The obtained
developing new lowtemperature processes of partial oxide particles were examined using a LEO1420
oxidation of various hydrocarbons [1–6] and of des scanning microscope and a LEO 906E transmission
ulfurization of hydrocarbon raw materials [7]. In this microscope. XRay diffraction analysis was performed
regard, a promising method for synthesizing molybde on a Carl Zeiss HZG4A diffractometer (Cu(Kα) radi
num–vanadium (Mo : V) oxides is the joint polycon ation). The IR spectra were recorded on a Thermo
densation of the corresponding oxoacids in an aque Nicolet Avatar 330 FTIR spectrometer. The assign
ous medium, which makes it possible to prepare dis ment of the bands of the IR spectra was carried out
persed phases with a strictly predetermined structural, based on the data from [2, 10–12].
dimensional, and morphological characteristics [7–9].
The EPR spectra were recorded in 3.0mmdiam
For example, carrying out the polycondensation under
eter quartz ampules at 77 using a Bruker EMX8
atmospheric pressure (i.e., under solvothermal condi
Xband spectrometer operated at a modulation fre
tions) yielded isomorphically substituted oxide phases
quency of 100 kHz. The parameters of the spin Hamil
exhibiting a high activity in the reaction of selective
tonian for the V(IV) ions were calculated as recom
oxidation of thiophene in organic solvents [7].
mended in the monograph [13]. The number of para
The purpose of this study was to establish the pecu magnetic centers in the samples was evaluated by
liarities of the formation of mixed Mo : Voxides dur double integration of the spectra with subsequent
ing the copolycondensation of molybdic acid and comparison of the results with a reference, the spec
vanadium in the aqueous medium at an elevated pres trum of a CuCl2 ⋅ 2H2O single crystal with known num
sure. ber of spins.

721
722 BARABOSHINA et al.

4 μm 1 μm 20 μm
(a) (b) (c)

500 nm 500 nm 1 μm
(a') (b') (c')

Fig. 1. SEM (top) and TEM (bottom) images of vanadium–molybdenum mixed oxide phases produced by hydrothermal synthe
sis at a pressures of (a, a') 5, (b, b') 10, and (c, c') 20 MPa.

RESULTS AND DISCUSSION peaks within 480–500 cm–1, corresponding to the

According to electron microscopy analysis (Fig. 1), bending vibrations of the –V–O– bond, and peaks
at elevated pressures, the formation of homogeneous within 680–740 cm–1 (frequencies lower than that of
highly porous structures with pore size up to several the –V–O–V– bridge bond (756 cm–1)), which
microns occurs in the reaction medium containing presumably belong to the stretching vibrations of
mixed molybdenumvanadium acids. When the pres the –V–O–Mo– bond, are indicative of the presence
sure increases to 20 MPa, these structures tend to of a large number of molybdenum atoms isomorphi
degenerate into wellfaceted needlelike structures with cally substituting vanadium atoms in the V2O5 xerogel.
an average length of 30 µm, which only rarely combine Note that, when vanadium atoms in the V2O5 structure
into agglomerates. The major structural elements of are substituted by molybdenum atoms, part of the
both highly porous cellular structures formed at 5 and vanadium atoms change their valence state from V(V)
10 MPa and extended formations arising at 20 MPa are to V(IV), as evidenced by the presence of a shoulder of
needles 0.5–5.0 µm in size (Fig. 1). the 967cm–1 absorption peak, which belongs to the
The results of Xray analysis show that the oxide stretching vibration of the V(IV)=O bond. That the
phases formed are solid solutions based on a xerogel of tested samples contain hybrid structures formed by a
hydrated vanadium pentoxide with an admixture of partial substitution of cationic positions in the V2O5
hexagonal molybdenum trioxide; i.e., they have the structure by molybdenum atoms is also seen from the
same phase composition as mixed Mo : V oxides pre splitting of most of the bands in the IR spectra. This
pared by solvothermal method at atmospheric pres effect observed for the mixed oxide phases synthesized
sure [7, 9] (Fig. 2). With increasing pressure, the at low pressure (5 MPa), but practically undetectable
degree of crystallinity of the mixedoxide phase for the samples prepared at high pressure (20 MPa).
increases sharply, while manifestations of the separa
tion of the individual MoO3 phase become more pro As the pressure of hydrothermal synthesis is raised,
nounced (Fig. 2). the manifestations of individual MoO3 (through
According to IR spectroscopy, all the dispersed absorption bands at ~970 cm–1, Mo=O stretching vibra
phases formed during the hydrothermal synthesis are tion; ~900 cm–1, –Mo–O–Mo– stretching vibration;
characterized by a high content of physically and and ~500 cm–1, –Mo–O– bending vibration) become
chemically bound water and by a large number of ter increasingly pronounced (Fig. 3). This separation of
minal hydroxyl groups (Fig. 3), as is indicated by the the hexagonal MoO3 phase upon pressure rise, which
absorption peaks in the frequency ranges 1405–1620 is also clearly seen from diffractograms (Fig. 2), can be
and 3495–3580 cm–1. We can conclude that the oxala explained by the fact that the solid solutions of oxides
tion processes responsible for the formation of the produced by isomorphic substitution are thermody
xerogel remain largely uncompleted. IR absorption namically less stable (due to a weakening of the

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 9 No. 5 2015

 MOLYBDENUM–VANADIUM MIXED OXIDES SYNTHESIZED 723

(a)
7000

6000

5000

4000

3000

2000

1200
(b)

1000

800

600

400

200

10° 20° 30° 40° 50° 60° 70°

2θ

Fig. 2. Diffractograms of molybdenum–vanadium mixed oxide phases synthesized at (a) 5 and (b) 20 MPa; (䊉) MoO3 and
(䊏)V2O5 xerogel.

bonds), and therefore, they degenerate at harsher syn (Fig. 4, spectra 3, 4) [7, 9, 14] and by the thermal
thesis conditions. decomposition of coprecipitated ammonium meta
Further information on the valence state of the molybdate and metavanadate (Fig. 4, spectra 5, 6), [5,
molybdenum and vanadium ions and their spatial 15, 16]. It was shown [7, 9, 15] that, even at relatively
organization in the samples was obtained by the EPR low vanadium concentrations, the EPR spectra of
method. Figure 4 shows typical EPR spectra at 77 K of mixed Mo : V oxides (Fig. 4, spectrum 5) exhibit no
mixed molybdenum–vanadium oxides (V : Mo = 1 : 1) features belonging to Mo(V) or Mo(III) paramagnetic
prepared at 5 and 20 MPa by using the hydrothermal ions. Thus, vanadium ions oxidize the reduced states
method. Both spectra are inhomogeneously broad of molybdenum formed during the synthesis, for
ened asymmetric singlet lines with an effective gfactor example, due to photochemical processes [17].
of g0 = 1.975 ± 0.005 and a line width ΔH0 of (8.6 ± The EPR spectra in Fig. 4 indicate that, at a suffi
0.7) mT at 5 MPa and (6.5 ± 0.5) mT at 20 MPa. Sim ciently high concentration of vanadium in the sample,
ilar EPR spectra were previously observed for mixed areas with very high local concentrations of V(IV)
Mo : V oxides synthesized by the solvothermal method paramagnetic centers (magnetically concentrated

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 9 No. 5 2015

724 BARABOSHINA et al.

2
3
1

2 5

300 350 400

В, mT

Fig. 4. EPR spectra at 77 K (normalized in amplitude) of

molybdenum–vanadium mixed oxides (V : Mo = 1 : 1)
1 synthesized by the hydrothermal method at (1) 5 and
(2) 20 MPa; (3, 5) by the solvothermal method, and (4) by
the thermal decomposition of coprecipitated salts. For
sample 5, V : Mo = 1 : 10.

magnetic. Note that, in the oxides synthesized by the

hydrothermal method (Fig. 4, spectra 1 and 2), the
4000 3000 2000 1000 fraction of isolated V(IV) ions is even smaller, 5%.
Wavenumber, cm–1 The results of the present study suggest that carry
ing out the polycondensation synthesis at an elevated
Fig. 3. IR spectra of molybdenum–vanadium mixed oxide pressure produces only a negligible effect on the struc
phases synthesized at (1) 5, (2) 10, and (3) 20 MPa.
tural features of the resulting oxide phases, which
appears to be an isomorphically substituted V2O5 xero
associates) arise, which being involved in a strong gel with a MoO3 admixture unsolved in the V2O5
static spin–exchange interaction with each other, pro matrix. At the same time, increasing the pressure sig
duce a singletization of the EPR spectra [18–20]. That nificantly affects the habitus of synthesized crystals by
the shape of the EPR spectrum is different and ΔH0 is inhibiting their twodimensional growth (i.e., sup
smaller for the sample prepared at a pressure of pressing the formation of layered crystals with low
20 MPa, as compared to the sample of the same com aspect ratio), so that onedimensional growth begins
position prepared at 5 MPa (Fig. 4, spectra 1 and 2) is to dominate, thereby producing needlelike structures.
indicative of a stronger spinexchange between V(IV) This effect, in turn, leads to the formation of mixed
paramagnetic ions in the sample synthesized at 20 MPa, oxide phases with a high surfacetovolume ratio, so
that increasing the pressure of hydrothermal synthesis
which can be accounted for by a higher local concen
of Mo : V oxides can be regarded as a specific dispers
tration of V(IV) ions and, accordingly, a smaller aver
ing factor.
age distance between them.
The authors are grateful to the Center for Magnetic
The lowintensity lines observed in spectra 3 and 4 Spectroscopy of the Institute of Biochemical Physics
(Fig. 4) suggest that these samples, along with areas of the Russian Academy of Sciences for recording
with a high local concentration of V(IV) ions, contain EPR spectra.
isolated V(IV) centers (~25–30% of the available
V(IV) ions) (Fig. 4, spectra 3–5). In the studied sam This work was supported by the Russian Founda
ples, more than 80% of the vanadium ions are para tion for Basic Research (project no. 140390020 Bela)

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 9 No. 5 2015

 MOLYBDENUM–VANADIUM MIXED OXIDES SYNTHESIZED 725

and the Belarusian Republican Foundation for Fun 11. A. I. Kharlamov, Rep. Nat. Acad. Sci. Ukraine, No. 4,
damental Research (grant no. H14R076). 148 (2007).
12. M. A. Vuurman, D. J. Stufkens, A. Oskam, G. Deo,
and I. E. Wachs, J. Chem. Soc., Faraday Trans. 92, 3259
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