Preparation of Mixed Phase (Anatase/Rutile) TiO2 Nanopowder by Simple Sol Gel Method
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The document details the preparation of mixed phase (anatase/rutile) TiO2 nanopowder using a simple sol-gel method, resulting in an average crystallite size of 35 ± 5 nm. Characterization through X-ray diffraction (XRD), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) confirms thermal stability and phase structure. The study proposes further exploration of gas sensing behavior for applications in photocatalysis and gas sensing due to the improved properties of the mixed phase TiO2.
![International Journal of Latest Technology in Engineering, Management & Applied Science (IJLTEMAS)
Volume VI, Issue II, February 2017 | ISSN 2278-2540
www.ijltemas.in Page 25
Preparation of Mixed Phase (Anatase/Rutile) TiO2
Nanopowder by Simple Sol Gel Method
Shubhra Mathur1#
, Rohit Jain#
, S.K. Sharma*
#
Department of Physics, JaganNath Gupta Institute of Engineering & Technology, Jaipur, 302022, India
*
Department of Physics, Malaviya National Institute of Technology, Jaipur, 302017, India
Abstract- TiO2 nanopowder having both anatase and rutile
phases was prepared by a simple procedure using sol-gel method.
Titanium isopropoxide was used as a titania source and mixed
with methanol and TiO2 nanopowder was obtained after
annealing at 6000
C for 1 hour in air. The specimens made from
this powder were characterized by X-ray diffraction (XRD),
Thermogravimetric analyzer (TGA) and Transmission electron
microscopy (TEM). XRD studies revealed the presence of both
anatase and rutile phases with an average crystallite size of 35 ±
5 nm. No significant weight loss up to 7000
C was observed by
TGA curve which indicates that TiO2 nanopowder is thermally
stable. TEM revealed the presence of a number of crystalline
grains in a structured matrix and selected electron diffraction
pattern showed different arrangement of diffracted rings which
confirms a phase evolution of crystalline grains of TiO2
(anatase/rutile) due to thermal annealing. Mixed phase
(anatase/rutile) TiO2 nanopowder has been reported [1], [2] to
exhibit improved photocatalytic and gas sensing properties. It is
proposed to study the gas sensing behavior of these specimens
during our research investigations on TiO2 nanopowder.
Key words: Sol-gel, TiO2, anatase, rutile, XRD
I. INTRODUCTION
iO2 is an important semiconductor material due to its
wide range of applications in various fields such as
photocatalysis, gas sensing, solar energy conversion etc [3],
[4]. The phases of TiO2 are anatase, rutile, and brookite.
Among them rutile is a high temperature stable phase whereas
anatase and brookite are metastable phases and transform to
rutile on heating [5]. Mixed phase TiO2 (anatase/rutile)
nanopowder leads to improvement in photocatalytic and gas
sensing properties [1], [2]. Thus it will be beneficial to obtain
TiO2 mixed phase (anatase/rutile) nanopowder by a simple
sol-gel method. With this motivation the present study was
undertaken.
In our investigation we optimize the synthesis
method of TiO2 nanopowder by changing the quantity of
titanium isopropoxide which leads to a mixed phase
(anatase/rutile) TiO2 nanopowder with a reduced crystallite
size at a lower annealing temperature as compared to data
reported in the literature [4].
II. EXPERIMENTAL
3.5 ml of titanium isopropoxide is mixed with 40 ml
methanol which results in a milky white solution. This
solution is stirred vigorously using magnetic stirrer for 1:30
hrs. at a temperature about 57±30
C. Thus the gel produced is
kept for 12 hrs. at room temperature for drying. The powder
obtained is collected and annealed at 6000
C for 1 hr. in air.
This results in the formation of mixed phase (anatase/rutile)
TiO2 nanopowder with an average crystallite size of 35±5 nm
as revealed by XRD [4].
III. RESULTS
Fig. 1 shows X-ray diffraction pattern (XRD) of TiO2
recorded using CuKα radiation. Diffraction peaks showing the
presence of both anatase and rutile phase are seen. The
diffraction angles are in good agreement with the JCPDS card
no 21-1272 for anatase, 21-1276 for rutile and the data
reported in literature [5], [6], [7].
101A
20 30 40 50 60 70
301R
204A+002R
211A
200A
105A+211R
103A
004A
112A
110R
Intensity(arb)
2 Thetha
TiO2
A- Anatase
R-Rutile
Fig. 1: X-ray diffraction pattern (XRD) of TiO2 nanopowder.
T](https://image.slidesharecdn.com/25-27-170301090337/85/Preparation-of-Mixed-Phase-Anatase-Rutile-TiO2-Nanopowder-by-Simple-Sol-Gel-Method-1-320.jpg)
![International Journal of Latest Technology in Engineering, Management & Applied Science (IJLTEMAS)
Volume VI, Issue II, February 2017 | ISSN 2278-2540
www.ijltemas.in Page 26
Using Scherrer’s formula [6] the average crystallite size is
35±5 nm and the content of anatase and rutile phase is
calculated using formula Xa = 100/ 1+ 1.265 (Ir/Ia) where Xa is
the weight fraction of anatase in the mixture, Ia and Ir are
intensities of anatase (101) and rutile (110) diffraction peaks
[5]. In our investigation the content of anatase phase is about
97.27% whereas rutile phase is about 2.73%.
Thermogravimetric analysis (TGA) was carried out at a
heating rate of 100
C/min from 300
C to 7000
C in nitrogen
atmosphere for TiO2 nanopowder as shown in Fig. 2. It is
observed that there is no significant weight loss upto 7000
C
which indicates that the sample is thermally stable [8].
100 200 300 400 500 600 700
0
20
40
60
80
100
(weight%)
Temperature (
0
C)
Fig. 2: TGA of TiO2 nanopowder.
Fig 3 (a) shows TEM image of TiO2 nanopowder which
revealed the presence of a large number of crystalline grains
in a structured matrix and surface morphology of TiO2
nanopowder is shown in Fig.3 (b). Fig. 3 (c) represents
different arrangement of dominant diffracted rings which
confirms a phase evolution of crystalline grains of TiO2
(anatase/rutile) due to thermal annealing [4], [9].
Fig. 3 (a)
Fig. 3 (b)
Fig. 3 (c)
Fig. 3: TEM image (a) showing crystalline grains in structured matrix (b)
surface morphology (c) selected electron diffraction pattern of TiO2
nanopowder
IV. DISCUSSION
X-ray diffraction pattern of specimen prepared using simple
procedure in the present study shows the presence of both
anatase and rutile phase with an average crystallite size of
35±5 nm. This is also supported by TEM investigations.
Further, the specimens exhibit thermal stability till 7000
C. It is
noteworthy that specimen with mixed phase of anatase/rutile
of TiO2 have been reported to show improved photocatalytic
activity as compared to pure phases and even a small fraction
of rutile phase along with anatase enhances photocatalytic
activity [2]. Further it is reported that mixed phase
(anatase/rutile) TiO2 thin film annealed at 7000C may lead to
improvement in gas sensing characteristics of NH3 [4].
Enachi et al. [1] observed that an individual TiO2 nanotube
with anatase/rutile crystal structure exhibits better gas
response to H2 at room temperature. Therefore synthesis of
mixed phase TiO2 by simple sol gel method may be employed
to prepare specimens for these investigations. It is proposed to
study the gas sensing behavior of these specimens during our
research investigations on TiO2 nanopowder.](https://image.slidesharecdn.com/25-27-170301090337/85/Preparation-of-Mixed-Phase-Anatase-Rutile-TiO2-Nanopowder-by-Simple-Sol-Gel-Method-2-320.jpg)
![International Journal of Latest Technology in Engineering, Management & Applied Science (IJLTEMAS)
Volume VI, Issue II, February 2017 | ISSN 2278-2540
www.ijltemas.in Page 27
V. CONCLUSION
1. TiO2 nanopowder having anatase/rutile phase with an
average crystallite size of 35±5 nm was prepared by simple
sol-gel method.
2. TGA curve depicts no significant weight loss upto 7000
C
which indicates that TiO2 nanopowder is thermally stable.
ACKNOWLEDGEMENT
Authors thank Science & Engineering Research Board
(SERB) for providing financial grant vide
SERB/F/5303/2014-15 and MRC, MNIT, Jaipur for
characterization facilities.
REFERENCES
[1]. Enachi, M., Lupan, O., Braniste, T., Sarua, A., Chow, L., Mishra,
Y. K., Gedamu, D., Adelung, R., Tiginyanu, I., (2015). Integration
of individual TiO2 nanotube on the chip: nanodevice for hydrogen
sensing. Phys. Status Solidi RRL 2015, 1-4.
[2]. Singh, J., Mohapatra, S., (2015) .Thermal evolution of structural,
optical and photocatalytic properties of TiO2 nanostructures. Adv.
Mater. Lett. 6(10), 924-929.
[3]. Hanaor, D.A.H., Sorrell, C.C., (2011). Review of the anatase to
rutile phase transformation. J. Mater. Sci. 46, 855-874.
[4]. Pawar, S., Chougule, M., Patil, S., Raut, B., Dalvi, D., Patil, P.,
Sen, S., Joshi, P., Patil, V., (2011). Fabrication of nanocrystalline
TiO2 thin film ammonia vapor sensor. Journal of Sensor
Technology 1, 9-16.
[5]. Dai, S., Wu, Y., Sakai, T., Du, Z., Sakai, H., Abe, M., (2010).
Preparation of highly crystalline TiO2 nanostructures by acid-
assisted hydrothermal treatment of hexagonal structured
nanocrystalline titania/cetyltrimethyammonium bromide
nanoskeleton. Nanoscale Research Letters 5, 1829-1835.
[6]. Vijayalakshmi, K., Rajendran, V., (2012). Synthesis and
characterization of nano-TiO2 via different methods. Archives of
Applied Science Research 4(2), 1183-1190.
[7]. Vijayalakshmi, K., Rajendran, K. V., (2010). Effect of K+
doping
on the phase transformation of TiO2 nanoparticles. AZojomo 6,
DOI : 10.2240/azojomo0298.
[8]. Wang, Y., Jia, W., Strout, T., Ding, Y., Lei, Y., (2009).
Preparation, characterization and sensitive gas sensing of
conductive core-sheath TiO2-PEDOT nanocables. Sensors 9,
6752-6763.
[9]. Parveen, A., Roy A.S., (2013). Effect of morphology on thermal
stability of core-shell polyaniline/TiO2 nanocomposites. Advanced
Materials Letters 4(9), 696-701.](https://image.slidesharecdn.com/25-27-170301090337/85/Preparation-of-Mixed-Phase-Anatase-Rutile-TiO2-Nanopowder-by-Simple-Sol-Gel-Method-3-320.jpg)
Preparation of Mixed Phase (Anatase/Rutile) TiO2 Nanopowder by Simple Sol Gel Method
- 1. International Journal of Latest Technology in Engineering, Management & Applied Science (IJLTEMAS) Volume VI, Issue II, February 2017 | ISSN 2278-2540 www.ijltemas.in Page 25 Preparation of Mixed Phase (Anatase/Rutile) TiO2 Nanopowder by Simple Sol Gel Method Shubhra Mathur1# , Rohit Jain# , S.K. Sharma* # Department of Physics, JaganNath Gupta Institute of Engineering & Technology, Jaipur, 302022, India * Department of Physics, Malaviya National Institute of Technology, Jaipur, 302017, India Abstract- TiO2 nanopowder having both anatase and rutile phases was prepared by a simple procedure using sol-gel method. Titanium isopropoxide was used as a titania source and mixed with methanol and TiO2 nanopowder was obtained after annealing at 6000 C for 1 hour in air. The specimens made from this powder were characterized by X-ray diffraction (XRD), Thermogravimetric analyzer (TGA) and Transmission electron microscopy (TEM). XRD studies revealed the presence of both anatase and rutile phases with an average crystallite size of 35 ± 5 nm. No significant weight loss up to 7000 C was observed by TGA curve which indicates that TiO2 nanopowder is thermally stable. TEM revealed the presence of a number of crystalline grains in a structured matrix and selected electron diffraction pattern showed different arrangement of diffracted rings which confirms a phase evolution of crystalline grains of TiO2 (anatase/rutile) due to thermal annealing. Mixed phase (anatase/rutile) TiO2 nanopowder has been reported [1], [2] to exhibit improved photocatalytic and gas sensing properties. It is proposed to study the gas sensing behavior of these specimens during our research investigations on TiO2 nanopowder. Key words: Sol-gel, TiO2, anatase, rutile, XRD I. INTRODUCTION iO2 is an important semiconductor material due to its wide range of applications in various fields such as photocatalysis, gas sensing, solar energy conversion etc [3], [4]. The phases of TiO2 are anatase, rutile, and brookite. Among them rutile is a high temperature stable phase whereas anatase and brookite are metastable phases and transform to rutile on heating [5]. Mixed phase TiO2 (anatase/rutile) nanopowder leads to improvement in photocatalytic and gas sensing properties [1], [2]. Thus it will be beneficial to obtain TiO2 mixed phase (anatase/rutile) nanopowder by a simple sol-gel method. With this motivation the present study was undertaken. In our investigation we optimize the synthesis method of TiO2 nanopowder by changing the quantity of titanium isopropoxide which leads to a mixed phase (anatase/rutile) TiO2 nanopowder with a reduced crystallite size at a lower annealing temperature as compared to data reported in the literature [4]. II. EXPERIMENTAL 3.5 ml of titanium isopropoxide is mixed with 40 ml methanol which results in a milky white solution. This solution is stirred vigorously using magnetic stirrer for 1:30 hrs. at a temperature about 57±30 C. Thus the gel produced is kept for 12 hrs. at room temperature for drying. The powder obtained is collected and annealed at 6000 C for 1 hr. in air. This results in the formation of mixed phase (anatase/rutile) TiO2 nanopowder with an average crystallite size of 35±5 nm as revealed by XRD [4]. III. RESULTS Fig. 1 shows X-ray diffraction pattern (XRD) of TiO2 recorded using CuKα radiation. Diffraction peaks showing the presence of both anatase and rutile phase are seen. The diffraction angles are in good agreement with the JCPDS card no 21-1272 for anatase, 21-1276 for rutile and the data reported in literature [5], [6], [7]. 101A 20 30 40 50 60 70 301R 204A+002R 211A 200A 105A+211R 103A 004A 112A 110R Intensity(arb) 2 Thetha TiO2 A- Anatase R-Rutile Fig. 1: X-ray diffraction pattern (XRD) of TiO2 nanopowder. T
- 2. International Journal of Latest Technology in Engineering, Management & Applied Science (IJLTEMAS) Volume VI, Issue II, February 2017 | ISSN 2278-2540 www.ijltemas.in Page 26 Using Scherrer’s formula [6] the average crystallite size is 35±5 nm and the content of anatase and rutile phase is calculated using formula Xa = 100/ 1+ 1.265 (Ir/Ia) where Xa is the weight fraction of anatase in the mixture, Ia and Ir are intensities of anatase (101) and rutile (110) diffraction peaks [5]. In our investigation the content of anatase phase is about 97.27% whereas rutile phase is about 2.73%. Thermogravimetric analysis (TGA) was carried out at a heating rate of 100 C/min from 300 C to 7000 C in nitrogen atmosphere for TiO2 nanopowder as shown in Fig. 2. It is observed that there is no significant weight loss upto 7000 C which indicates that the sample is thermally stable [8]. 100 200 300 400 500 600 700 0 20 40 60 80 100 (weight%) Temperature ( 0 C) Fig. 2: TGA of TiO2 nanopowder. Fig 3 (a) shows TEM image of TiO2 nanopowder which revealed the presence of a large number of crystalline grains in a structured matrix and surface morphology of TiO2 nanopowder is shown in Fig.3 (b). Fig. 3 (c) represents different arrangement of dominant diffracted rings which confirms a phase evolution of crystalline grains of TiO2 (anatase/rutile) due to thermal annealing [4], [9]. Fig. 3 (a) Fig. 3 (b) Fig. 3 (c) Fig. 3: TEM image (a) showing crystalline grains in structured matrix (b) surface morphology (c) selected electron diffraction pattern of TiO2 nanopowder IV. DISCUSSION X-ray diffraction pattern of specimen prepared using simple procedure in the present study shows the presence of both anatase and rutile phase with an average crystallite size of 35±5 nm. This is also supported by TEM investigations. Further, the specimens exhibit thermal stability till 7000 C. It is noteworthy that specimen with mixed phase of anatase/rutile of TiO2 have been reported to show improved photocatalytic activity as compared to pure phases and even a small fraction of rutile phase along with anatase enhances photocatalytic activity [2]. Further it is reported that mixed phase (anatase/rutile) TiO2 thin film annealed at 7000C may lead to improvement in gas sensing characteristics of NH3 [4]. Enachi et al. [1] observed that an individual TiO2 nanotube with anatase/rutile crystal structure exhibits better gas response to H2 at room temperature. Therefore synthesis of mixed phase TiO2 by simple sol gel method may be employed to prepare specimens for these investigations. It is proposed to study the gas sensing behavior of these specimens during our research investigations on TiO2 nanopowder.
- 3. International Journal of Latest Technology in Engineering, Management & Applied Science (IJLTEMAS) Volume VI, Issue II, February 2017 | ISSN 2278-2540 www.ijltemas.in Page 27 V. CONCLUSION 1. TiO2 nanopowder having anatase/rutile phase with an average crystallite size of 35±5 nm was prepared by simple sol-gel method. 2. TGA curve depicts no significant weight loss upto 7000 C which indicates that TiO2 nanopowder is thermally stable. ACKNOWLEDGEMENT Authors thank Science & Engineering Research Board (SERB) for providing financial grant vide SERB/F/5303/2014-15 and MRC, MNIT, Jaipur for characterization facilities. REFERENCES [1]. Enachi, M., Lupan, O., Braniste, T., Sarua, A., Chow, L., Mishra, Y. K., Gedamu, D., Adelung, R., Tiginyanu, I., (2015). Integration of individual TiO2 nanotube on the chip: nanodevice for hydrogen sensing. Phys. Status Solidi RRL 2015, 1-4. [2]. Singh, J., Mohapatra, S., (2015) .Thermal evolution of structural, optical and photocatalytic properties of TiO2 nanostructures. Adv. Mater. Lett. 6(10), 924-929. [3]. Hanaor, D.A.H., Sorrell, C.C., (2011). Review of the anatase to rutile phase transformation. J. Mater. Sci. 46, 855-874. [4]. Pawar, S., Chougule, M., Patil, S., Raut, B., Dalvi, D., Patil, P., Sen, S., Joshi, P., Patil, V., (2011). Fabrication of nanocrystalline TiO2 thin film ammonia vapor sensor. Journal of Sensor Technology 1, 9-16. [5]. Dai, S., Wu, Y., Sakai, T., Du, Z., Sakai, H., Abe, M., (2010). Preparation of highly crystalline TiO2 nanostructures by acid- assisted hydrothermal treatment of hexagonal structured nanocrystalline titania/cetyltrimethyammonium bromide nanoskeleton. Nanoscale Research Letters 5, 1829-1835. [6]. Vijayalakshmi, K., Rajendran, V., (2012). Synthesis and characterization of nano-TiO2 via different methods. Archives of Applied Science Research 4(2), 1183-1190. [7]. Vijayalakshmi, K., Rajendran, K. V., (2010). Effect of K+ doping on the phase transformation of TiO2 nanoparticles. AZojomo 6, DOI : 10.2240/azojomo0298. [8]. Wang, Y., Jia, W., Strout, T., Ding, Y., Lei, Y., (2009). Preparation, characterization and sensitive gas sensing of conductive core-sheath TiO2-PEDOT nanocables. Sensors 9, 6752-6763. [9]. Parveen, A., Roy A.S., (2013). Effect of morphology on thermal stability of core-shell polyaniline/TiO2 nanocomposites. Advanced Materials Letters 4(9), 696-701.