J. Am. Ceram. Soc.
, 90 [12] 4030–4032 (2007)
Journal
Novel Low-Temperature Synthesis of Disodium Dimolybdate by
Ultrasonic Spray Pyrolysis
Dragana J. Jovanović, Ivana Lj. Validmić, Ivana A. Janković, Željka M. Andrić, Miodrag Mitrić,
and Jovan M. Nedeljkovićw
A new method for the synthesis of disodium dimolybdate
(Na2Mo2O7) in the process of ultrasonic spray pyrolysis using
acidified aqueous solutions of thermodynamically stable
molybdenum (VI) oxide clusters as a precursor is described.
Na2Mo2O7 particles were collected in alcohols (ethanol, 2-prop-
anol, isobutyl alcohol), and ultracentrifugation was used to iso-
late solid material from solution. Scanning electron microscopy
revealed the formation of uniform spherical Na2Mo2O7 particles
with an average diameter of about 0.25 lm. The X-ray diffrac-
tion analysis undoubtedly confirmed the formation of ortho-
rhombic Na2Mo2O7 for samples synthesized at a temperature as
low as 3001C.
I. Introduction
T ERNARY compounds of Na–M–O (M 5 Ni, Mo, and Fe) are
formed and involved in the corrosion of structural stainless
steel in coolant circuits of liquid sodium-cooled fast breeder
reactors. Because molybdenum is an important fission product
and is formed in large amounts in the nuclear fission of U and
Pu (fission yield around 20%), the fuel–coolant interaction can
lead to the formation of one or more ternary Na–Mo–O com-
pounds. The development of simple synthetic routes for the
preparation of phase-pure Na–Mo–O compounds is a prereq-
uisite in order to study their phase relations and thermodynamic
properties.1,2
The conventional method for preparation of disodium dim-
olybdate (Na2Mo2O7) is thermal treatment of a mixture con-
sisting of sodium molybdate and molybdenum trioxide in a
platinum crucible for 2 weeks at 7001C.3 In the meantime, Goel
and Mehrotra4 reported on the preparation of Na2Mo2O7 dur-
ing the process of pyrolysis of sodium oxomolybdenum (VI)
oxalate at a lower temperature (2801C). To the best of our
knowledge, no other papers concerning the synthesis of Na2
Mo2O7 can be found in the literature. On the other hand, ul-
trasonic spray pyrolysis (USP) has been used for the synthesis of
molybdenum oxide films, mainly molybdenum trioxide.5–7 In
principle, USP has been used for the preparation of particles of
the desired morphology and structure on a large scale, using
either ionic species or colloidal nanoparticles as a precursor.8–11
Recently, an aqueous solution consisting of silver iodide com-
plex species has been used as a precursor in the process of USP
in order to obtain submicronic AgI particles with the desired
morphology.12
In this paper, a new low-temperature method for the synthesis
of Na2Mo2O7 in the process of USP using acidified aqueous
P. S. Patil—contributing editor
Manuscript No. 23281. Received May 30, 2007; approved August 1, 2007.
Supported by the Ministry of Science and Environmental Protection of the Republic of
Serbia under grant 142066.
w
Author to whom correspondence should be addressed. e-mail: jovned@vin.bg.ac.yu
4030
DOI: 10.1111/j.1551-2916.2007.02047.x
r 2007 The American Ceramic Society
VinWa Institute of Nuclear Sciences, 11001 Belgrade, Serbia
solutions of thermodynamically stable molybdenum (VI) oxide
clusters as a precursor is described. This method is rather
unexplored, and thermodynamically stable molybdenum (VI)
oxide clusters have never been used for this purpose before.
Aqueous species of molybdenum (VI) have a complex chemistry
due to various protonation and polymerization equilibria de-
pending on the experimental conditions like pH and concentra-
tion.13,14 However, the system that we used is well characterized
and mainly consists of two dominant complex species (Mo7O624
and Mo8O426 ).15 Under specific experimental conditions of syn-
thesis, the formation of a pure orthorhombic Na2Mo2O7 phase
was found, while the particles obtained were spherical and quite
uniform in size.
II. Experimental Procedure
All chemicals (molybdenum (VI) oxide, perchloric acid, isobutyl
alcohol, 2-propanol, ethanol, and sodium perchlorate) pur-
chased from Merck (Darmstadt, Germany) were of the highest
purity available and they were used without further purification.
Aqueous solutions of thermodynamically stable molybdenum
(VI) oxide clusters were prepared as described in the literature.16
Briefly, molybdenum (VI) oxide solutions were prepared at
pH 5 3.9 (adjusted by HClO4) and at a constant ionic strength
of 3M (adjusted by NaClO4). The typical total molybdate con-
centration in the solution was 0.1M.
The Na2Mo2O7 powders were obtained in the process of USP
using solutions consisting of molybdenum (VI) oxide clusters as
the starting material. The laboratory setup for USP consists of
an ultrasonic atomizer (GAPUSOL-RBI-91-012, Sarl, France)
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 working temperatures were in the range
from 2001 to 4001C, while the effective heating length of the
reactor tube was 1 m. The flow rate of air was 30 dm3/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 obtained were collected in different
alcohols (isobutyl alcohol, 2-propanol, ethanol), and particles
were separated from solvent containing excess of Cl ions im-
mediately after synthesis using ultracentrifugation. Synthesized
Na2Mo2O7 particles were washed several times with appropriate
alcohol and dried at 3001C for about 1 h.
Absorption spectra of the precursor solution were measured
using a UV-Vis spectrophotometer (Perkin Elmer Lambda 5,
Waltham, MA). The reflection spectra of Na2Mo2O7 powder
were recorded using an Avantes S2000 (Eerbeek, the Nether-
lands) instrument with a deuterium—–halogen light source.
Scanning electron microscopy (SEM) measurements were
performed using a JEOL JSM-6460LV instrument (Tokyo,
Japan). The Na2Mo2O7 samples were coated with a thin layer
of gold deposited by a sputtering process. The thickness of the
gold film was up to 40–50 nm.
December 2007 Communications of the American Ceramic Society 4031

The X-ray diffraction (XRD) measurements were carried out

on a Philips PW-1050 (Eindhoven, the Netherlands) automatic
diffractometer using CuKa radiation. Measurements were per-
formed in the 2y range from 101 to 801 with a scanning step
width of 0.021 and a time of 10 s per step.

III. Results and Discussion

Aqueous species of molybdenum (VI) have a complex chemis-
try, and they are formed in a number of overlapping and
simultaneously existing protonation–deprotonation and aggre-
gation–disaggregation equilibria that can be reached from either
direction.13–15 The appearance of different molybdenum (VI)
species depends mainly on the total molybdate concentration
and the degree of acidification of the solution. It should be
pointed out that there are many reaction models proposing the
existence of many different polyoxometalate species.15,16 The
system chosen for this study (total molybdate concentration of
0.1M and pH 5 3.9) is well characterized in the literature,15 and
under the above-mentioned conditions Mo7O624 and Mo8O426
species exist at a concentration level of more than 90% of the
total molybdate concentration. For the sake of clarity, only
Mo7O624 and Mo8O426 species will be considered as precursors in
the process of USP.
An absorption spectrum of the precursor solution consisting
of thermodynamically stable molybdenum (VI) oxide clusters is
shown in Fig. 1 (curve a). The absorption spectrum is rather
featureless, with two shoulders in between 330 and 340 nm and a
tail toward the visible spectral region. It has been found using
analytical ultracentrifugation that larger clusters absorb at long-
er wavelengths.16–18 The featureless reflection spectrum of Na2
Mo2O7 powder obtained after the process of USP is also shown
in Fig. 1 (curve b). It can be noticed that the decrease of the
reflection intensity of Na2Mo2O7 powder starts at 440 nm. This
value is red shifted for about 70 nm compared with the absorp-
tion onset (370 nm) of the precursor solution.
Clusters of molybdenum oxide were, for the first time, used as
the starting material in the process of USP. During the process
of USP, the sprayed droplets containing molybdenum oxide
clusters were transformed into particles by different processes
including solvent evaporation and precipitation of the dissolved
substance. A typical SEM image of the Na2Mo2O7 particles
collected after the USP in 2-propanol and separated from the
solvent by ultracentrifugation is shown in Fig. 2. Most of the
particles were spherical with a fairly uniform size distribution.
The average diameter was found to be around 0.25 mm. The
Na2Mo2O7 particles collected either in 2-propanol, ethanol, or
isobutyl alcohol had similar size distributions. Fine tuning of the
average diameter of Na2Mo2O7 particles can be achieved by
changing the frequency of the atomizer. The dependence
Fig. 2. Typical scanning electron microscopy image of disodium
dimolybdate particles (scale bar 1 mm).
between particle diameter and frequency is given elsewhere.19
It should be mentioned that the conventional method developed
by Seleborg3 led to the formation of rod-shaped Na2Mo2O7
crystals.
Solid materials obtained after the process of USP were ana-
lyzed using XRD measurements. A typical XRD spectrum of
Na2Mo2O7 powder collected in isobutyl alcohol, thoroughly
washed, and dried at 3001C is shown in Fig. 3. The XRD anal-
ysis clearly showed on orthorhombic crystalline structure of
Na2Mo2O7 (JCPDS No. 76-0185). The most intensive planes on
the XRD spectrum are indexed. It should be pointed out that
samples dried at room temperature are not amorphous,
although the XRD peaks are less pronounced. No traces of
any other crystalline phase were noticed in the Na2Mo2O7 sam-
ples collected in isobutyl alcohol and prepared at a temperature
not lower than 3001C. On the other hand, small amounts of
impurities (o5%) were present in samples collected either in 2-
propanol or ethanol. We identified these impurities as MoO3
and Na2O2. This is not surprising keeping in mind that a variety
of molybdenum (VI) complex species participate as a starting
material during the course of Na2Mo2O7 synthesis.
IV. Summary
In this work, we presented a new low-temperature approach for
the synthesis of Na2Mo2O7 based on the process of USP
using acidified aqueous solutions of thermodynamically stable

Fig. 1. Absorption spectrum of the precursor solution at pH 5 3.9, and

the total molybdate concentration of 0.1M (a). Reflection spectrum of Fig. 3. X-ray diffraction pattern of disodium dimolybdate (Na2Mo2O7)
disodium dimolybdate powder (b). powder obtained during the process of ultrasonic spray pyrolysis.
4032 Communications of the American Ceramic Society
molybdenum (VI) oxide clusters as a precursor. SEM revealed
the formation of uniform spherical Na2Mo2O7 particles with
average diameter of about 0.25 mm, while the XRD analysis
undoubtedly confirmed formation of orthorhombic Na2Mo2O7
for samples synthesized at a temperature as low as 3001C. De-
tailed structural characterization of the synthesized material is
underway in our laboratory.
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