Advanced Materials Research Vols. 183-185 (2011) pp 2254-2257
Online available since 2011/Jan/20 at www.scientific.net
© (2011) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.183-185.2254
Preparation, characterization of nonmetal doped TiO2 nanoparticles
with their excellent photocatalystic properties
WANG Ying-Wei1,a ，LI Yu-Fei 1,b,YANG Pei-Han2,c
1
College of Forestry, Northeast Forestry University, Harbin, 150040,China,
2
a
Environmental Protection Agency , Suifenhe City ,157300,China
[email protected], [email protected] ,[email protected]
Keywords: Titania; Photocatalyst; Nonmental; Calcination
Abstract. Nonmetal (S, P) doped titania nanoparticles were synthesized by a one step hydrothermal
method. These samples were calcined with different temperature, the sample exist in anatase phase
has much higher photocatalytic activity for methylene blue (MB) degradation. The visible response
and the higher UV activity of the different nonmetal doped TiO2 make it possible to utilize solar
energy efficiently to execute photocatalysis processes. The resulting materials were characterized by
X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), etc. It can conclude the
nonmetal doping TiO2 proves to be more suitable to improve the photocatalytic performance.
Introduction
The photocatalyst decompose pollutants in water and air has attracted much interest for decades
. Ever since, heterogeneous photocatalysis by means of TiO2 has been widely accepted and
exploited as an efficient technology for killing bacteria and degrading organic and inorganic
pollutants [2,3]. But, the extensive exploitation of TiO2 created an expectation to use merely 3–4%
UV light of the whole radiant solar energy because of its wide band gap. A number of promising
ways to design a second generation of visible-light-sensitive photocatalysts of titanium dioxide [4,5].
Li et al. synthesized N–F codoped TiO2 photocatalysts by spray pyrolysis (SP) using TiCl3 and
NH4F precursors [6]. Luo et al. prepared a Br and Cl codoped TiO2 system and demonstrated the
efficiency of the material for photocatalytic splitting of water into H2 and O2 [7]. These recent efforts
and strategies have revealed that codoping TiO2 with a metal and a nonmetal can result in the
development of additional visible active photocatalysts. [8]
Our previous work demonstrated that the modulation of the textural and optical properties could
be accomplished by the modification with sulfur and phosphorus. In this paper, we will use
calcination method to synthesis S-doped titania, P-doped titania, and then, campared with the
photocatalytic activity and the morphology (crystalline size, texture, etc.) of them.
[1]
Experiment
In the process of phosphorus doped TiO2 , we need Tetrabutyl titanate 10 ml, ethanol 20 ml and
acetic acid 4 ml. The first step, 10 g tetrabutyl titanate was dissolved in 10ml of ethanol under slow
stirring at room temperature. Then we can get the mixture, which was labeled as solution A. The
second step, 10 ml of ethanol, 4 ml of acetic acid and some phosphoric acid was mixed to form a
All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of TTP,
www.ttp.net. (ID: 130.203.136.75, Pennsylvania State University, University Park, USA-10/03/15,06:21:22)
Advanced Materials Research Vols. 183-185
2255
homogeneous solution, which was labeled as solution B. The P/TiO2 molar ratio in the resulting
suspension was 0.1. A stable and transparent colloid solution can be obtained by dropping the
solution B into the solution A under vigorous stirring. And then the mixture was dried at 80 ºC for
about 24 h to vaporize water and alcohol in the gels. The synthesized xerogel samples were calcined
at 450ºC, 550ºC, 650ºC and 800ºC for 6h, to obtain phosphor-doped titania CPT. The S-doping
samples, which use the Thio Urea (500mg) was synthesised by the same process. And the
photocatalysic properties of the P-doping samples were tested by the degradation of the methylene
blue (MB), and S-doping was tested by the degradation of organophosphorus pesticide, and was
calcined by 450ºC, 500ºC, 600ºC.
Results and discussion
As we can see from Fig.1 ,the sample of S-doping calcined at 600ºC has the highest degradation
ability. And the ones calcined at 450ºC has little degradation efficiency. The visable light
absorbance was considerable improved with the calcination temperature rising, so TiO2 doping with
sulfur at a high calcination temperature can improve not only the performance of the spectrum
absorption but also the efficiency of the photocatalytic degradation.
Degradation rate / %
60
50
40
30
20
10
0
0
20
40
60
80
100
light irradiation time [min]
120
Fig.1 the degradation rate of organophosphorus pesticide under xenon lamp irradiation
2256
Environmental Biotechnology and Materials Engineering
1.4
CPT 450
P-TiO 2
transmittance [a. u.]
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0
20
40
60
80
100
light irradiation time [min]
Fig.2 The degradation rate of MB under xenon lamp irradiation
The photocatalytic properties of P-doping can be seen at the Fig.2. The sample calcined at
800ºC has the highest degradation ability. And the ones calcined at 450ºC has a little degradation
efficiency. The degradation rare was considerable increased with the calcination temperature rising,
so TiO2 doping with phosphorous at a high calcination temperature can get a better photocatalytic
property.
Fig.3 The XRD patterns of P-doping with different calcination
From the Fig.3, The diffraction patterns reveal anatase phase with preferential (101) plane and
the diffraction peaks of Ti substrate in 450 °C, 550°C, and 650°C. So P-doping improved the
thermal stability of titania and prevented the phase transformation of anatase to rutile. And when
the temperature go up to 800°C, the diffraction peak transform to rutile phase.
Advanced Materials Research Vols. 183-185
2257
Conclusions
We have used a calcinaton method to obtain the S doped and P doped TiO2 power successfully. In
this work, the sample of S-doping calcined at 600ºC has the highest degradation ability. The highly
photoactive P-doped TiO2 prepared by calcined at 650°C still in the anatase phase and calcined at
800ºC has the highest degradation ability. P-doping improved the thermal stability of titania and
prevented the phase transformation of anatase to rutile.
References
[1] O. Legrini, E. Oliveros, A. Braun: Chem. Rev. Vol. 93 (1993) p.671.
[2] P.-C. Maness, S. Smolinski, D.M. Blake, Z. Huang, E.J. Wolfrum, W.A.Jacoby: Appl. Environ.
Microbiol. Vol. 65 (1999) , p 4094.
[3] T.L. Thomson, D.A. Panayotov, J.T. Yates Jr., I. Martyanov, K. Klabunde:J. Phys. Chem.
B.Vol. 108 (2004) , p 17875.
[4] M. Anpo, M. Takeuchi: J. Catal. 216 (2003) , p 505.
[5] H. Yamashita, M. Takeuchi, M. Anpo: Encyclopedia Nanosci, Nanotechnol. Vol. 10 (2004) , p
639.
[6] D. Li, H. Haneda, S. Hishita, N. Ohashi: Chem. Mater. Vol. 17 (2005) , p 2596.
[7] H. Luo, T. Takata, Y. Lee, J. Zhao, K. Domen, Y. Yan: Chem. Mater. Vol. 16 (2004) , p 846.
[8] Y. Sakatani, H. Ando, K. Okusako, H. Koike: J. Mater. Res. Vol. 19 (7) (2004) , p 2100.
Environmental Biotechnology and Materials Engineering
10.4028/www.scientific.net/AMR.183-185
Preparation, Characterization of Nonmetal Doped TiO2 Nanoparticles with their Excellent
Photocatalystic Properties
10.4028/www.scientific.net/AMR.183-185.2254
DOI References
[1] O. Legrini, E. Oliveros, A. Braun: Chem. Rev. Vol. 93 (1993) p.671.
doi:10.1002/chin.199328333
[3] T.L. Thomson, D.A. Panayotov, J.T. Yates Jr., I. Martyanov, K. Klabunde:J. Phys. Chem. .Vol. 108
(2004) , p 17875.
doi:10.1016/j.cplett.2004.09.083
[4] M. Anpo, M. Takeuchi: J. Catal. 216 (2003) , p 505.
doi:10.1163/156856703322539654
[6] D. Li, H. Haneda, S. Hishita, N. Ohashi: Chem. Mater. Vol. 17 (2005) , p 2596.
doi:10.1016/j.nimb.2005.03.071
[7] H. Luo, T. Takata, Y. Lee, J. Zhao, K. Domen, Y. Yan: Chem. Mater. Vol. 16 (2004) , p 846.
doi:10.1021/cm035090w
[8] Y. Sakatani, H. Ando, K. Okusako, H. Koike: J. Mater. Res. Vol. 19 (7) (2004) , p 2100.
doi:10.1557/JMR.2004.0269
[2] P.-C. Maness, S. Smolinski, D.M. Blake, Z. Huang, E.J. Wolfrum, W.A.Jacoby: Appl. Environ.
Microbiol. Vol. 65 (1999) , p 4094.
doi:10.1080/03602549909351643
[3] T.L. Thomson, D.A. Panayotov, J.T. Yates Jr., I. Martyanov, K. Klabunde:J. Phys. Chem. B.Vol. 108
(2004) , p 17875.
doi:10.1016/j.cplett.2004.09.083