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Materials Chemistry and Physics 99 (2006) 394–397

A rapid synthesis of sodium titanium phosphate, NaTi2(PO4)3


by using microwave energy
Halil Güler ∗ , Figen Kurtuluş
Department of Chemistry, Faculty of Arts and Sciences, Balıkesir University, 10100 Balıkesir, Turkey
Received 16 May 2005; received in revised form 5 October 2005; accepted 11 November 2005

Abstract
In this study, sodium titanium phosphate, NaTi2 (PO4 )3 was synthesized in a pure form by using microwave energy. The NaTi2 (PO4 )3 was
obtained by mixing the initial reactants of TiO2 , (NH4 )2 HPO4 and NaH2 PO4 ·2H2 O with the molar ratio of 2:2:1 in a domestic type of microwave
oven by using 2.45 GHz frequencies and at power of 750 W. The reaction was completed in 15 min. The microwave heating process was achieved
by the help of the NaH2 PO4 ·2H2 O which is the only microwave absorber in the initial mixture. The product was analyzed by X-ray diffraction
(XRD) and fourier transform infra red (FT-IR) techniques and the results confirms the rhombohedral crystal structure of the NaTi2 (PO4 )3 with the
unit cell parameters of a = 8.4913(3), c = 21.7858(12) Å, space group R3̄c and Z:6. The titled compound is also known as a member of NASICON
materials. In future, it is possible to synthesize different types of sodium including NASICON compounds by the help of microwave susceptor
agent of the NaH2 PO4 ·2H2 O.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Microwave synthesis; NASICON compounds; NaTi2 (PO4 )3 ; Metal phosphates

1. Introduction pounds could be prepared in many different routes, recently the


microwave method has been become an alternative method since
1.1. Metal phosphates and NASICON compounds the reaction time is very short comparing to the traditional tech-
niques.
Metal phosphates continue to be of great interest as they are
used in a variety of commercial, industrial and scientific applica- 1.2. Microwave assisted material synthesis
tions. Recently, NaTi2 (PO4 )3 was also accepted as a member of
NASICON compounds (acronym for Sodium (Na) super ionic Microwaves are electromagnetic radiation, whose wave-
conductor). Goodenough et al. [1] have demonstrated that the lengths lie in the range of 1 mm to 1 m (frequency range of
skeleton of the NASICON materials behave as fast ion con- 0.3–300 GHz). Only narrow frequency windows centered at
ductors. They also behave as good ionic conductors when they 900 MHz and 2.45 GHz are allowed for microwave heating pur-
serve as solid-state electrolytes. These type of materials have poses. Very few microwave applications involving heating have
also been proposed for use as a solid-electrolyte in solid-state been reported for frequencies of 28, 30, 60 and 83 GHz [5–8].
electrochemical devices such as gas sensors, ion sensors and In order to initiate and drive a microwave-assisted reaction, at
Na–S batteries [2–4]. least one of the initial reactants must couple with the microwave
The metal phosphates are usually synthesized by conven- field.
tional methods. The solid-state reactions between the reactants Many microwave preparations reported in the literature have
are usually taking placed at high temperatures (usually between been done on the laboratory scale of only a few grams. These
∼700 and 1500 ◦ C) and also needs long reaction time in the syntheses have all been made with the use of domestic type of
muffle type furnaces. Although, many metal phosphate com- microwave ovens which operates at 2.45 GHz with a maximum
output power of 1 kW. Moreover, use of higher power levels for
specific applications has also been reported [6,8-11]. Nowadays,
∗ Corresponding author. Tel.: +90 2662493358; fax: +90 2662456366. large industrial types of microwave furnaces are manufactured
E-mail address: hguler@balikesir.edu.tr (H. Güler). for the production of many chemicals in larger quantities.

0254-0584/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2005.11.011
H. Güler, F. Kurtuluş / Materials Chemistry and Physics 99 (2006) 394–397 395

1.3. Microwave heating with the assistance of homogenous mixture was obtained. The mixture was transferred into a ceramic
NaH2 PO4 ·2H2 O crucible and exposed to microwave energy in the microwave oven for 15 min.
As a final stage, sample was allowed to cool inside the oven for 30 min. The
experiment was repeated several times for reproducibility test.
Vaidhyanathan et al. reported [12] a novel microwave-
assisted route for the preparation of sodium rich binary
metal phosphates in the form of crystalline or glassy phases. 3. Results and discussion
Microwave radiation is expected to activate the rotation
degrees of freedom for H2 O molecules present in the sam- 3.1. Evaluation of the XRD pattern of the synthesized
ple NaH2 PO4 ·2H2 O. The sample first melts and then it forms NaTi2 (PO4 )3
a highly concentrated solution of NaH2 PO4 . In the second
stage, the H2 O molecules escape from the solution leaving When the initial reactants were exposed to microwave radi-
behind “hot” NaH2 PO4 , which behaves as microwave absorb- ation, in a minute, the water molecule was evoporated from the
ing agent itself. This material then continues to be heated even reactants. Then, flashes were seen in the center of mixture. At the
further where upon in the third stage, the water which chem- end of this process, redness from the reactants in the ceramic cru-
ically bounded to NaH2 PO4 was eliminated from the sam- cible was observed. The approximate temperature was estimated
ple. After 5 min, the temperature of this process was mea- between the ranges of 700 and 900 ◦ C. At this temperature, a
sured as 678 ◦ C [12]. A solid-state reaction could be occurred solid–solid reaction occurred between the initial reactants. This
between NaH2 PO4 ·2H2 O and other possible reactants. Using chemical reaction could be explained by the following equation:
this method, different type of binary and/or quaternary metal 2TiO2 + 2(NH4 )2 HPO4 + NaH2 PO4 ·2H2 O
phosphates could be synthesized purely and economically.
→ NaTi2 (PO4 )3 + 2NH3 (g) + 6H2 O(g)
1.4. Synthesis of the NaTi2 (PO4 )3
The XRD pattern of the synthesized sample belongs to the
compound, NaTi2 (PO4 )3 and the data was in excellent agree-
In the literature, the synthesis of the titled compound,
ment with the JCPDS card no. 33-1296 (Fig. 1). The title com-
NaTi2 (PO4 )3 was reported in the JCPDS card no 33-1296
pound has rhombohedral crystal structure with the cell parame-
which was prepared by heating a 1:2:2 molar mixture of
ters of a = 8.4913(3) Å and c = 21.7858(12) Å. The space group
NaH2 PO4 ·2H2 O, (NH4 )2 HPO4 and TiO2 (anatase) at 1000 ◦ C.
is R3̄c and Z is six. For comparison, the literature and experi-
The obtained sample was then reground and heated at 1200 ◦ C
mental XRD values were given in Table 1.
for 18 h. The detail XRD data of this sample was given in the
JCPDS card.
In this work, we have developed a previously unreported 3.2. Evaluation of the FT-IR spectrum of NaTi2 (PO4 )3
microwave-assisted synthesis route for the sodium titanium
phosphate, NaTi2 (PO4 )3 . It was obtained purely in a short IR spectrums of the experimental product of NaTi2 (PO4 )3
time (15 min) by using microwave electromagnetic radiation was given in Fig. 2. The functional groups of the experi-
(2.45 GHz, 750 W). mental data are also listed in Table 2. The stretching modes
of a free PO4 −3 anion with Td symmetry have four internal
2. Experimental modes of vibrations [13–15] which are ν3 (PO4 ) = 1107, 1024;
ν1 (PO4 ) = 954; ν4 (PO4 ) = 576; ν2 (PO4 ) = 482 cm−1 . These
2.1. Chemical substances vibrational wave numbers are in reasonable agreement with

The reagents, TiO2 , (NH4 )2 HPO4 and NaH2 PO4 ·2H2 O were used as initial
reactants for the synthesis of NaTi2 (PO4 )3 . All commercial reagents were of
analytical grade and supplied from the Merck company.

2.2. Instruments

Microwave-assisted reactions were carried out with a domestic type of


microwave oven, Arçelik MD-560. The oven was operated at 2.45 GHz fre-
quency with a power of 750 W.
The X-ray powder diffraction data were collected by a diffractometer,
Brucker AXS-ADVANCED-DX with a position sensitive detector, graphite
monochromator and Cu K␣ radiation (40 kV, 20 mA and λ = 1.54056 Å). Infrared
spectrum was obtained using a Perkin-Elmer BX-2 FT-IR spectrometer in the
4000–400 cm−1 region with sample as KBr discs.

2.3. Procedures

Sodium titanium phosphate, NaTi2 (PO4 )3 was synthesized by mixing the


initial reactants of TiO2 , (NH4 )2 HPO4 and NaH2 PO4 ·2H2 O with the molar Fig. 1. X-ray powder diffraction pattern of the synthesized product of
ratio of 2:2:1. The weighted samples were grounded in an agate mortar until a NaTi2 (PO4 )3 .
396 H. Güler, F. Kurtuluş / Materials Chemistry and Physics 99 (2006) 394–397

Table 1
The literature and observed XRD data of the synthesized product of NaTi2 (PO4 )3 (JCPDS card no. 33-1296)
hkl I Iobs d dobs hkl I Iobs d dobs

012 14 13 6.095 6.086 312 1 1 2.0053 2.0051


104 20 21 4.3770 4.384 128 15 10 1.9455 1.9451
110 32 27 4.2450 4.249 134 3 3 1.9100 1.8990
113 100 100 3.6660 3.669 0 2 10 2 2 1.8740 1.8690
006 10 5 3.6320 3.631 315 2 2 1.8473 1.8470
202 4 6 3.4850 3.483 226 16 10 1.8330 1.8335
024 28 22 3.0480 3.048 0 0 12 5 4 1.8152 1.8150
116 64 50 2.7590 2.760 042 6 4 1.8128 1.8119
(2 1 1) (64) (50) (2.7590) (2.760) 404 <1 <1 1.7419 1.7411
122 2 1 2.6940 2.701 2 1 10 9 5 1.7144 1.7145
018 1 1 2.5530 2.556 137 7 4 1.7058 1.7056
214 2 2 2.4761 2.4755 321 <1 <1 1.6821 1.6825
300 16 10 2.4520 2.4510 232 1 1 1.6674 1.6693
208 2 2 2.1883 2.189 318 6 3 1.6328 1.6322
119 7 5 2.1032 2.1040 324 5 2 1.6115 1.6113
217 2 2 2.0733 2.0739 410 11 5 1.6048 1.6030
223 5 4 2.0378 2.0375 229 2 2 1.5959 1.6001
306 6 5 2.0322 2.0327 235 2 3 1.5733 1.5734
(1 3 1) (6) (5) (2.0322) (2.0327) 413 2 3 1.5670 1.5668

Microwave processing is a relatively new method in material


processings. The coupling efficiency of microwaves directly to
the material is the primary advantage of microwave process-
ing as compared to traditional routes. The volumetric heating
ability of microwaves allows for more rapid and uniform heat-
ing, resulting in decreased processing time, and often enhanced
material properties.
The NaTi2 (PO4 )3 is also known as a member of NASI-
CON materials, so, in future, it is possible to synthesize
sodium including NASICON compounds with or without dop-
ing any metal ions by the help of microwave absorbing agent of
NaH2 PO4 ·2H2 O. Recently, since industrial types of microwave
ovens are produced by manufacturers, these microwave synthe-
Fig. 2. IR spectrum of the synthesized product of NaTi2 (PO4 )3 . ses techniques could easily adapted to the industrial processes
in future.
Table 2
IR spectrum data of the synthesized product of NaTi2 (PO4 )3
Acknowledgement
Assignments Frequency (cm−1 ) NaTi2 (PO4 )3

ν3 (PO4 ) 1132 This work has been supported by Balıkesir University with
ν1 (PO4 ) 1026 research project foundation contracts numbers: 2000-08 and
νS (POP) 638 2002-12.
ν4 (PO4 ) 568
␯2 (PO4 ) 430
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