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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.
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
2.3. Procedures
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
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
References
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