J. Am. Ceram. Soc.
, 92 [10] 2467–2470 (2009)
Journal
Structure of Disodium Dimolybdate Synthesized Using Thermo-
dynamically Stable Molybdenum (VI) Oxide Clusters as Precursors
Dragana J. Jovanović, Ivana Lj.Validmić, Miodrag Mitrić, and Jovan M. Nedeljkovićw
The structure of disodium dimolybdate (Na2Mo2O7) synthesized
by a low-temperature method in the process of ultrasonic spray
pyrolysis using acidified aqueous solutions of thermodynami-
cally stable molybdenum (VI) oxide clusters as a precursor was
refined down to an R-factor of 7%. The refinement of the
diffraction data showed that Na2Mo2O7 powder synthesized
at 3001C belongs to the base-centered orthorhombic type of
structure with a space group of Cmca (no. 64). It was found that
the basic units of the octahedral MoO6 precursor complexes
exist in the structure of Na2Mo2O7. Tetrahedral MoO4 building
units that coexist together with octahedral units in the structure
of Na2Mo2O7 are most likely developed by the termination of
weak octahedral bonds and by the placement of the molybdenum
atom in the center of the tetrahedra.
I. Introduction
S O far, ultrasonic spray pyrolysis (USP) has been used for the
preparation of particles of a desired morphology and struc-
ture on a large scale using either ionic species or colloidal
nanoparticles as a precursor.1,2 On the other hand, recently,
an aqueous solution consisting of AgI clusters was used in the
process of USP in order to study the influence of solvent, aging
time, and the structure of the starting complexes on the mor-
phological and structural properties of the AgI particles.3,4 This
method is rather unexplored and, to the best of our knowledge,
this was the first time that clusters of such a small agglomeration
number were used as a starting material in the process of USP.
Recently, a new low-temperature method for the synthesis of
Na2Mo2O7 in the process of USP using acidified aqueous
solutions of thermodynamically stable molybdenum (VI) oxide
clusters as a precursor has been reported.5 Aqueous species of
molybdenum (VI) have a complex chemistry due to various
protonation and polymerization equilibria, depending on the
experimental conditions like pH and concentration.6 However,
the used system is well characterized and mainly consists of two
dominant complex species, Mo7O6 4 7
24 and Mo8O26 , which con-
tain octahedral MoO6 monomers (showing meshing and exten-
sion of the MoO4 tetrahedral building units) that are linked at
their vertexes. The vertexes linked in the clusters share an
oxygen atom.8,9 On the other hand, the structure of Na2Mo2O7
is described as infinite chains formed from MoO6 octahedra
sharing vertexes within the chains, while MoO4 tetrahedra
bridge adjacent MoO6 groups.10
In this paper, the refinement of the crystal structure of the
Na2Mo2O7 powder was reported. The Na2Mo2O7 was synthe-
sized using molybdenum (VI) oxide clusters as a precursor in
C. Sorrell—contributing editor
Manuscript No. 25769. Received February 2, 2009; approved May 27, 2009.
Financial support for this study was granted by the Ministry of Science and Techno-
logical Development of the Republic of Serbia (Project 142066).
w
Author to whom correspondence should be addressed. e-mail: jovned@vin.bg.ac.yu
2467
DOI: 10.1111/j.1551-2916.2009.03225.x
r 2009 The American Ceramic Society
VinWa Institute of Nuclear Sciences, 11001 Belgrade, Serbia
the process of USP at the lowest possible temperature in order
to avoid the formation of agglomerated particles. It was
shown that the basic unit of the starting complexes’ octahedral
MoO6 monomer remains preserved in the Na2Mo2O7 powder.
Tetrahedral building units of Na2Mo2O7 are formed by the
termination of weak octahedral bonds of the precursor and by
the placement of the molybdenum atom in the center of the
tetrahedra.
II. Experimental Procedure
All chemicals (Na2MoO4  2H2O (498%), perchloric acid
(70%–72%), isobutyl alcohol (99.5%), and NaClO4  H2O
(99%)) were purchased from Merck (Darmstadt, Germany)
and used without further purification. Aqueous solutions of
thermodynamically stable molybdenum (VI) oxide clusters were
prepared as described in the literature.5 Briefly, molybdenum
(VI) oxide solutions were prepared at a pH 5 3.9 (adjusted by
HClO4) and at a constant ionic strength of 3M (adjusted by
NaClO4  H2O). The total molybdate concentration in the solu-
tion was 0.1M.
The Na2Mo2O7 powders were obtained in the process of
USP, as described elsewhere.5 Briefly, the laboratory set-up for
USP consists of an ultrasonic atomizer (GAPUSOL-RBI-91-
012) operating at a frequency of 1.7 MHz for aerosol generation,
and a horizontal electric furnace with a quartz tube and a vessel
for particle collection. The effective heating length of the reactor
tube was 1 m (the length of the whole tube is 1.3 m, and the
cross-sectional area of the tube is 11.94 cm2), with the maximum
temperature of 3001C in the middle of the furnace. The flow rate
of air was 3 m3/h. The flow rate of aerosol droplets was assumed
to be equal to the flow rate of the gas carrier, and the residence
time of aerosol droplets in the furnace was found to be 1 min.
The Na2Mo2O7 powders were collected in isobutyl alcohol,
because a powder with the smallest percent of impurities was
obtained in this alcohol, as described in detail previously.5 In
order to remove the excess of electrolytes, the particles were
separated from the isobutyl alcohol immediately after synthesis
by using ultracentrifugation. Synthesized Na2Mo2O7 particles
were washed several times with isobutyl alcohol and dried at
3001C for about 1 h.
The X-ray powder diffraction (XRPD) patterns of the in-
vestigated samples were obtained on a Philips PW-1050 auto-
mated diffractometer (Eindhoven, the Netherlands) using CuKa
radiation (operated at 40 kV and 30 mA). Fixed 11 divergence
and 0.11 receiving slits were used. Diffraction data for structural
analysis were collected in the 2y range 10–1201, counting for 12 s
in 0.021 steps. Structure analysis was performed by using the
KOALARIE computing program,11 based on the Rietveld full-
profile refinement method.12 This program is suitable to obtain
microstructural parameters such as crystallite size, microstrain,
and the R factor.11 Samples for XRPD measurements were
prepared using the standard protocol.13
2468 Communications of the American Ceramic Society Vol. 92, No. 10

Table I. The structure of Na2Mo2O7. Space Group: Cmca.10 Table II. Interatomic Distances and Angles in Na2Mo2O7
Unit Cell Dimensions: a 5 0.719448(19) nm, b 5 1.188698(36)
Mo–O +O–Mo–O
nm, c 5 1.475898(45) nm. Cell Content: 8 Na2Mo2O7
Atom Position X(s(X)) Y(s(Y)) Z(s(Z)) B(s(B)) Octahedron
1–5 5 1–50 0.2436(6) nm 5–1–50 80.0(2)1
Mo(1) 8(e) 1/4 0.0823(2) 1/4 0.48(5) 1–6 5 1–60 0.1772(7) nm 5–1–6 90.4(3)1
Mo(2) 8(f) 0 0.2481(2) 0.0848(1) 0.65(5) 1–8 5 1–80 0.1937(3) nm 5–1–60 169.7(3)1
Na(3) 8(f) 0 0.3174(6) 0.3416(5) 0.17(11) O–O mean 2.91 nm 5–1–8 75.2(3)1
Na(4) 8(d) 0.2429(19) 0 0 0.17(11) 5–1–80 91.6(3)1
O(5) 16(g) 0.2225(10) 0.2393(5) 0.1448(4) 1.72(18) 6–1–60 99.4(3)1
O(6) 16(g) 0.2103(14) 0.4859(5) 0.3395(5) 1.72(18) 6–1–8 89.5(4)1
O(7) 8(f) 0 0.3595(11) 0.5090(6) 1.43(22) 6–1–80 101.6(4)1
O(8) 8(f) 0 0.1065(9) 0.2947(6) 1.43(22) 8–1–80 162.9(5)1
O(9) 8(f) 0 0.4066(10) 0.0288(7) 1.43(22)
Tetrahedron
2–5 5 2–500 0.1832(7) nm 5–2–500 121.8(3)1
2–7 0.1700(12) nm 5–2–7 106.0(3)1
III. Results and Discussion 2–9 0.2058(11) nm 5–2–9 104.3(2)1
The refinement of the diffraction data showed that Na2Mo2O7 O–O mean 2.92 nm 7–2–9 115.1(5)1
powder belongs to the base-centered orthorhombic type of Na–O (octahedral arrangement)
structure. The structure refinements were performed in the space Na(3)–O mean 0.242 nm
group C2/m2/C21/a (no. 64). It is well known that sodium Na(4)–O mean 0.236 nm
dimolybdate crystallizes in structural types in which molybde-
num ions occupy two different crystallographic positions, 8(e)
[1/4y1/4] with local symmetry 2, and 8(f) [0yz] with local
symmetry m.10
Sodium ions also occupy two crystallographic positions, 8(f) For a tetrahedron, the Mo2–Mo2 distance was found to be
[0yz] with local symmetry m, and 8(d) [x00] with local symmetry 0.438 nm, while for Mo1–Mo2 it is 0.361 nm. The obtained
2. On the other hand, oxygen ions occupy three different values are almost identical to the data reported by Seleborg
crystallographic positions, the previously mentioned 8(f), and (0.358 and 0.360 nm for Mo1–Mo1 and Mo1–Mo2, respec-
two additional crystallographic positions, 16(g) [xyz] with local tively).10 Distances between the atoms presented in Table II
symmetry 1. Results of the final Rietveld refinements (the unit are in quite good agreement with distances found in the starting
cell dimensions) are presented in Table I and the final Rietveld Mo7O6 4
24 and Mo8O26 complexes
14
(0.250–0.290 nm for O–O;
plot is depicted in Fig. 1. The crystallite size and microstrain of 0.170, 0.190, 0.230 nm for Mo–O; and 0.320, 0.350, 0.420 nm for
the whole pattern are 160.25 nm and 0.10%, respectively. The Mo–Mo). All these results indicate that the basic units of the
structure of disodium dimolybdate was refined down to an R- starting complexes remain preserved in the structure of diso-
factor of 7%. Values of estimated standard deviations as well as dium dimolybdate.
reliability factors confirmed that these data are reliable and that Aqueous species of Mo (VI) have a complex chemistry as a
the structure was well refined. consequence of various protonation and polymerization equili-
Based on the fixed and refined fraction coordinates of the bria.6,15,16 These species are formed in a number of overlapping
ions, selected distances and angles in Na2Mo2O7 (octahedron and simultaneously existing protonation and deprotonation,
and tetrahedron) were determined and presented in Table II. It aggregation and disaggregation equilibria, which can be reached
can be noticed that the tetrahedra are slightly distorted, while from either direction. Many different polyoxometalate species
the octahedra are considerably distorted. The obtained values were proposed so far, but on a speculative basis. However, the
are in good agreement with data reported by Seleborg.10 system that we used (total molybdate concentration of 0.1M and
Because of its relatively small size, hexavalent molybdenum pH 5 3.9) is well characterized in the literature.7 It was found by
has influence on the distortion of tetrahedral and octahedral using ultracentrifugation that under the above-mentioned con-
units, as pointed out by Seleborg.10 The Mo1–Mo1 distance in dition, Mo7O6 4
24 and Mo8O26 species are major components of
disodium dimolybdate for a MoO6 octahedron was found to be the system. Because of that, for the sake of clarity, in the further
0.360 nm. consideration we will assume that the precursor solution con-
tains only the above-mentioned clusters.
Molybdenum oxide clusters Mo7O6 4
24 and Mo8O26 are shown
in Figs. 2(A) and (B), respectively. As can be seen from the
resonance formula for polyoxometalate ions,9 the clusters are
1500 composed of MoO6 octahedral building units, in which the
metal is located in the center of the octahedra. Dashed and
solid lines in Fig. 2 represent weak and strong bonds of the
complex structure, respectively.9 The structure of Na2Mo2O7 is
intensity [a.u.]

1000
shown in Fig. 2(C). This structure can be described as built-up
of infinite chains formed from the MoO6 octahedra sharing
corners within the chains.10 The MoO4 tetrahedra are bridging
500 adjacent MoO6 units. Figure 2(C) demonstrates the connection
between the octahedral and tetrahedral building units. It is clear
from a comparison of the structures presented in Figs. 2(A) and
0
(B) with the structure presented in Fig. 2(C) that octahedrons
exist in the precursor clusters and the synthesized solid. Off
course, they are not identical.
20 40 60 80 100 However, Na2Mo2O7 also contains tetrahedral units. The
synthesis termination of weak octahedral bonds in the precursor
2θ [°]
species (dashed lines in Figs. 2(A) and (B)) leads to the forma-
Fig. 1. Final Rietveld plot of the Na2Mo2O7 powder. tion of tetrahedral building units. The placement of the molyb-
October 2009 Communications of the American Ceramic Society
Fig. 2. Resonance formula for Mo7O6 4
24 (A) and Mo8O26 (B) clusters. Schematic presentation of the Na2Mo2O7 structure (C).
denum atom in the center of the tetrahedron is probably enabled
by the presence of the sodium atom. It is clear that a correlation
between the structure of solid Na2Mo2O7 and the structures of
the complex precursor species exists.
The presence of a small amount of impurities (MoO3 and
Na2O2 o5%) can be explained, having in mind that a variety of
molybdenum (VI) complex species participate as precursors in
the course of Na2Mo2O7 synthesis.
IV. Summary
In this work we present the refinement of the crystal structure of
disodium dimolybdate powder obtained in the process of USP
using acidified aqueous solutions of thermodynamically stable
molybdenum (VI) oxide clusters as precursors. The basic,
octahedral units in the precursor complexes exist in the structure
of synthesized Na2Mo2O7. During the course of synthesis, at
elevated temperatures, the termination of weak octahedral
bonds in the complexes takes place and leads to the formation
of tetrahedral units, where the molybdenum atom was placed in
the center of the tetrahedra. It seems that the formation of solid
Na2Mo2O7 resembles the polymerization process of molybde-
num (VI) oxide clusters.
2469
References
1
J. M. Nedeljković, Z. V. Šaponjic, Z. RakoWević, and D. P. Uskoković,
‘‘Ultrasonic Spray Pyrolysis of TiO2 Nanoparticles,’’ Nanostruct. Mater., 9 [1–8]
125–8 (1997).
2
S. C. Tsai, Y. L. Song, C. S. Tsai, C. C. Yang, W. Y. Chiu, and H. M. Lin,
‘‘Ultrasonic Spray Pyrolysis for Nanoparticles Synthesis,’’ J. Mater. Sci., 39 [24]
3647–57 (2004).
3
I. Lj.Validmić, V. Jokanović, D. P. Uskoković, and J. M. Nedeljković,
‘‘Formation of Silver Iodide Particles from Thermodynamically Stable Clus-
ters Using Ultrasonic Spray Pyrolysis,’’ J. Eur. Ceram. Soc., 27 [2–3] 927–9
(2007).
4
I. Lj. Validmić, V. Jokanović, D. P. Uskoković, and J. M. Nedeljković,
‘‘Influence of Solvent on the Structural and Morphological Properties of AgI
Particles Prepared Using Ultrasonic Spray Pyrolysis,’’ Mater. Chem. Phys., 107 [1]
28–32 (2008).
5
D. J. Jovanović, I. Lj.Validmić, I. A. Janković, Ž. M. Andrić, M. Mitrić, and
J. M. Nedeljković, ‘‘Novel Low-Temperature Synthesis of Disodium Dimolyb-
date by Ultrasonic Spray Pyrolysis,’’ J. Am. Ceram. Soc., 90 [12] 4030–2
(2007).
6
K. H. Tytko, Gmelin Handbook of Inorganic Chemistry: Molybdenum, Vol. B3a,
8th edition, Springer, Berlin, 1987.
7
I. Lj.Validmić, G. van Hooijdonk, S. Oosterhout, and W. K. Kegel, ‘‘Thermo-
dynamic Stability of Clusters of Molybdenum Oxide,’’ Langmuir, 20 [8] 3435–40
(2004).
8
W. K. Kegel, ‘‘Equilibrium Clusters of Metal Oxides,’’ J. Phys. Chem. A, 108
[11] 1919–22 (2004).
9
K. H. Tytko, ‘‘A Bond Model for Polyoxometalate Ions Composed of
MO6 Octahedra (MOk Polyhedra with k44)’’; pp. 67–127 in Bonding and
Charge Distribution in Polyoxometalates: A Bond Valence Approach,
Vol. 93, Edited by M. J. Clarke, L. B. Goodenough, C. K. Jorgensen-D.M.P.
2470 Communications of the American Ceramic Society
Mingos, G. A. Palmer, P. J. Sadler, R. Weiss, and R. I. P. Williams. Springer,
Berlin, 1999.
10
M. Seleborg, ‘‘A Refinement of the Crystal Structure of Disodium Dimolyb-
date,’’ Acta Chem. Scand., 21, 499–504 (1967).
11
R. W. Cheary and A. A. Coelho, ‘‘A Fundamental Parameters Approach to
X-Ray Line-Profile Fitting,’’ J. Appl. Crystallogr., 25 [2] 109–21 (1992).
12
H. Rietveld, ‘‘A Profile Refinement Method for Nuclear and Magnetic
Structures,’’ J. Appl. Crystallogr., 2 [2] 65–71 (1969).
13
V. K. Pecharsky and P. Y. Zavalij, Fundamentals of Powder Diffraction and
Structural Characterization of Materials, Chapter 3, pp. 292–3. Springer, Berlin, 2005.
Vol. 92, No. 10
14
D. G. Lyxell, L. Pettersson, and I. Persson, ‘‘Multicomponent Polyanions. 57.
Large-Angle X-Ray Scattering Study of Aqueous Molybdophenylphosphonate
Solutions,’’ Inorg. Chem., 40 [4] 584–92 (2001).
15
K. H. Tytko, G. Baethe, and J. J. Cruywagen, ‘‘Equilibrium Studies of
Aqueous Polymolybdate Solutions in 1 M Sodium Chloride Medium at 251C,’’
Inorg. Chem., 24 [20] 3132–6 (1985).
16
J. J. Cruywagen and A. G. Draaijer, ‘‘Solvent Extraction Investigation of
Molybdenum (VI) Equilibria,’’ Polyhedron, 11 [2] 141–6 (1992). &