Synthesis and study of sodium vanadomanganate

Article abstract of DOI:10.1134/S0036023607120108

Sodium 13-vanadomanganate Na₇[MnV₁₃O ₃₈]?5H₂O (I) has been synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of compound I are monoclinic: a = 11.487 ?, b = 7.613 ?, c = 11.359 ?, β = 114.15°, V = 906.52 ?³, ρ_calcd = 2.73 g/cm³, Z = 1.

Full text of DOI:10.1134/S0036023607120108

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2007, Vol. 52, No. 12, pp. 1864–1867. © Pleiades Publishing, Inc., 2007.
Original Russian Text © G.Z. Kaziev, A.V. Oreshkina, S. Holguin Quinones, T.Yu. Glazunova, D.A. Alekseev, E.G. Cruz Fernandez, 2007, published in Zhurnal Neorgan-
icheskoi Khimii, 2007, Vol. 52, No. 12, pp. 1979–1982.
SYNTHESIS AND PROPERTIES
OF INORGANIC COMPOUNDS
Synthesis and Study of Sodium Vanadomanganate
a
a
b
c
G. Z. Kaziev , A. V. Oreshkina , S. Holguin Quinones , T. Yu. Glazunova ,
a
b
D. A. Alekseev , and E. G. Cruz Fernandez
a
Moscow Pedagogical State University, ul. Radio 10a, Moscow, 107005 Russia
b
Universidad Autonoma Metropolitana—Azcapotzalco, Mexico
c
Moscow State University, Vorob’evy gory, Moscow, 119992 Russia
Received October 10, 2006
Abstract—Sodium 13-vanadomanganate Na [MnV O ] · 5H O (I) has been synthesized and studied by mass
7
13 38
2
spectrometry, thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of com-
3
pound I are monoclinic: a = 11.487 Å, b = 7.613 Å, c = 11.359 Å, β = 114.15°, V = 906.52 Å , ρ
=
calcd
3
2
.73 g/cm , Z = 1.
DOI: 10.1134/S0036023607120108
Heteropoly compounds (HPCs) are intricate coordi- mogravimetry. The elemental analysis data are given
nation compounds with a unique structure and diverse below.
properties [1]. Different viewpoints about the structure
and nature of HPCs have been rather completely cov-
ered in the literature [2–8]. The synthesis and physico-
chemical studies of new compounds and determination
of trends in the behavior of their properties at different
compositions and structures are significant for the
development of HPC chemistry.
For Na [MnV O ] · 5H O anal. calcd. (wt %): Na,
7
13 38
2
1
0.20; Mn, 3.48; V, 42.04; O, 38.55; H O, 5.70.
2
Found (wt %): Na, 10.05; Mn, 3.63; V, 43.06; O,
3
8.5; H O, 5.67.
2
Compound I was studied by X-ray powder diffrac-
tion analysis, IR spectroscopy, and thermogravimetry.
X-ray powder diffraction analysis was carried out
Interest in heteropolyvanadates is due to their prac-
tical use as catalysts in organic synthesis of bisphenols
on a Stoe IP automated diffractometer in the 2θ range
1
0°– 80°. The X-ray diffraction patterns were indexed
[9], which are stabilizers of polymers and oils [10].
using the Powder-2 program package.
The structures of heteropolyvanadates of manga-
The thermogravimetric study was carried out on a
Paulik–Paulik–Erdey Q-1500 derivatograph in the tem-
perature range 20–1000°ë at a heating rate of 10 K/min
for a weighed sample of 100 g. Calcined alumina
served as the standard.
nese of different composition have been studied [11,
2], and the formation of the structure of these com-
1
pounds depending on the synthesis conditions (pH,
temperature).
This work is devoted to the synthesis and study of
the physicochemical properties of sodium vanadoman-
ganate Na [MnV O ] · 5H O.
IR spectra of the compounds were recorded on a
Perkin-Elmer spectrophotometer in the range 200–
7
13 38
2
–1
4
000 cm . Samples were prepared as potassium bro-
mide pellets.
EXPERIMENTAL
Sodium vanadomanganate Na [MnV O ] · 5H O
I) was synthesized using a modified method [13]: a
RESULTS AND DISCUSSION
As shown by the thermogravimetric study (Fig. 1),
7
13 38
2
(
solution of manganese sulfate and sodium persulfate compound I has two endotherms. The first peak is
was added to a hot solution of sodium metavanadate observed at 120°C and corresponds to the removal of
acidified to pH 3 with nitric acid. The mixture was five molecules of water of crystallization, and the sec-
heated in a water bath until the volume was halved. The ond endotherm at 500°C indicates the HPC decomposi-
resulting solution was filtered and cooled in a desicca- tion. The scheme of thermal decomposition of com-
tor, and after several days bright orange crystals of pound I can be presented as follows:
sodium vanadomanganate precipitated, which were fil-
1
20°C
Na [MnV O ] · 5H O
tered off and recrystallized from hot water.
7
13 38
2
–5H O
2
5
00°C
The chemical composition of the synthesized com-
pound was determined by mass spectrometry, and the
content of water of crystallization was found by ther-
Na [MnV O ]
7
13 38
–
3/2 O2
4NaVO + 3NaV O + MnO .
3 3 8 2
1
864

SYNTHESIS AND STUDY OF SODIUM VANADOMANGANATE
1865
T, °C
I, %
1
00
∆
m
T
9
8
7
6
0
0
0
0
5
00°C
TG
DTA
50
4
3
2
1
0
0
0
0
0
10
20
30
40
50
60
θ, deg
1
20°C
2
Time
Fig. 2. Stick X-ray powder diffraction pattern of
Na [MnV O ] · 5H O.
Fig. 1. Thermal analysis curves of Na [MnV O ] · 5H O.
7
13 38
2
7
13 38
2
X-ray powder diffraction analysis was carried out
The X-ray diffraction patterns obtained at ambient
for both compound I and the products of its thermal temperature and after the thermal effect at 120°ë are
decomposition in order to confirm the individual char- identical and correspond to the initial compound
acter and purity of the synthesized compound (Fig. 2), whereas those obtained at 500°ë correspond to
thermolysis products (Fig. 3, Table 2), confirming the
proposed scheme of thermal decomposition of com-
pound I.
Na [MnV O ] · 5H O, to obtain crystallographic data,
7
13 38
2
and to analyze the thermal decomposition products. The
X-ray diffraction patterns were indexed using the Pow-
der-2 program package. The comparison of the obtained
X-ray diffraction patterns with the PCPDFWIN data-
Table 2. X-ray diffraction data for the thermal decomposition
base shows that compound I is free of possible admix- products
tures and has monoclinic crystals with the unit cell
PCPDFWIN
card number
parameters a = 11.487 Å, b = 7.613 Å, c = 11.359 Å,
2θ, deg
d, Å
I, %
Compound
3
β = 114.15°, V = 906.52 Å . The pycnometric density of
the compound found according to Syromyatnikov’s
method [14] is ρexp = 2.73 g/cm , and the number of for-
mula units is Z = 1. The X-ray diffraction data are pre-
sented in Fig. 2 and Table 1.
1
1
2
2
2.47
3.34
0.90
1.85
7.10
6.63
4.46
4.06
3.61
3.017
2.88
2.84
2.78
2.68
2.59
2.43
2.41
2.29
1.96
1.90
1.89
1.81
11
100
20
6
NaVO3
NaV O
32–1198
12–0676
12–0676
35–0436
32–1197
32–1198
49–0997
32–1197
32–1197
32–1197
12–0676
44–0142
44–0992
32–1197
49–0997
44–0142
32–1198
12–0676
3
3
8
8
8
NaV O
3
NaV O
3
Table 1. X-ray diffraction data for Na [MnV O ] · 5H O
24.62
60
10
44
14
41
35
20
49
45
8
NaVO3
7
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2
2
3
3
3
3
3
3
3
3
4
4
4
5
9.58
0.94
1.38
2.08
3.41
4.49
6.88
7.15
9.22
6.07
7.70
8.05
0.10
NaVO3
2
θ, deg
.81
0.68
d, Å
I, %
h
1
1
0
2
0
3
k
0
0
1
0
1
1
l
NaV O
3
8
9
10.54
17.95
0
NaVO3
NaVO3
NaVO3
1
1
2
2
3
9.60 100
1
0
3.45
1.48
4.09
0.36
7.63
4.79
4.28
3.41
21.98
5.31
2.36
2
2
NaV O
3
8
MnO2
11.16
1
2
MnO2
3
1.38
3.30
2.10
3
1
NaVO3
3
3
3
2.91
3.79
8.76
3.15
3.07
2.69
17.28
22.94
13.54
1
2
3
2
2
2
2
0
20
13
5
NaV O
3
8
MnO2
1
0
4
NaVO3
4
4
0.65
9.36
2.57
2.14
4.11
3
0
2
2
20
NaV O
3
12.50
8
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 52 No. 12 2007

1
866
KAZIEV et al.
I, %
00
1
9
8
7
6
0
0
0
0
1
2
3
5
4
3
2
1
0
0
0
0
0
0
1
0
15 20 25 30 35 40 45 50
2
55
θ, deg
Fig. 3. Stick X-ray powder diffraction pattern of the thermal decomposition products of compound I at 500°C: (1) NaVO3,
(
2) NaV O , and (3) MnO .
3
8
2
Transmission, %
8
8
7
7
6
6
5
5
4
4
3
3
5
0
5
0
5
0
5
0
5
0
5
0
4
000
3500
3000
2500
2000
1500
1000
500
ν, cm–
1
Fig. 4. IR spectrum of Na [MnV O ] · 5H O.
7
13 38
2
The IR spectra of HPCs were studied in detail in studied HPC confirms our assumption about their
15]. The IR spectrum of compound I (Fig. 4) contains resembling structures.
three groups of absorption bands at 400–1000 cm
[
–1
attributed to vibrations of different metal–oxygen
bonds of the complex heteropolyanion. According to
published data [16], vibrations of the terminal (multi-
ACKNOWLEDGMENTS
This work was supported in part by the Russian Foun-
dation for Basic Research, project no. 05-03-32432.
ple) V=O bonds of the cis-VO group in the heteropoly-
2
–1
anion appear as a doublet at 900–1000 cm . In our
–1
case, these are intense bands at 897 and 954 cm . The
REFERENCES
–1
bands at 450–600 cm are assigned to vibrations of dif-
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2
–
1
–1
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6
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7
13 38
2
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SYNTHESIS AND STUDY OF SODIUM VANADOMANGANATE
1867
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1
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