Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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Preparation and Characteristics of Visible-Light-Active $TiO_2-_xN_x$ Nanoparticles for Photocatalytic Activities

가시광 활성을 갖는 광촉매용 $TiO_2-_xN_x$ 나노입자의 제조 및 특성

  • Received : 2009.07.30
  • Accepted : 2009.10.24
  • Published : 2009.11.30
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Abstract

Visible-light-active $TiO_2-_xN_x$ nanoparticles with a homogeneous anatase crystalline structure were successfully prepared through a hydrolysis of $TiCl_4$ with ammonia solution. The samples were characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), $N_2$-sorption, and UV-vis diffuse reflectance spectra (DRS) techniques. The light absorption onset shifted from 390 nm on pure $TiO_2$ to the visible region at 530 nm on nitrogen-doped $TiO_2$. A clear decrease in the band gap was deduced from the DRS results. The photocatalytic activity was evaluated from the photodegradation of congo red solution under visible light irradiation. The photocatalyst showed the highest photocatalytic activity at an optimal value of nitrogen doping concentration. This was suggested that the nitrogen doping should have an important effects on the improvement of photocatalytic activity.

가시광 활성을 갖는 anatase 결정구조의 $TiO_2-_xN_x$ 나노입자를 암모니아 수용액에서 $TiCl_4$ 가수분해에 의해 제조하였다. 제조한 시료의 특성은 XRD, TEM, $N_2$-sorption 및 DRS로 분석하였다. 질소를 $TiO_2$에 도핑함으로써 광흡수 영역이 순수한 TiO2에 해당하는 390 nm에서 가시광 영역인 530 nm까지 이동하였다. DRS 분석결과로부터 $TiO_2-_xN_x$의 밴드갭이 감소하는 것을 유추할 수 있었다. 광촉매 활성은 가시광 조사하에서 congo red 분해로부터 평가하였다. 질소의 도핑 농도가 적절한 광촉매가 광촉매 활성이 가장 높게 나타났다. 이러한 결과로부터 질소 도핑이 광촉매 활성의 향상에 중요한 역할을 함을 확인할 수 있었다.

Keywords

References

  1. Linsebigler, A. L., Lu, G., and Yates, J. T.,“ Photocatalysis on $TiO_{2}$ Surfaces: Principles, Mechanisms, and Selected Results,” Chem. Rev., 95(3), 735-758(1995) https://doi.org/10.1021/cr00035a013
  2. Hoffmann, M. R., Martin, S. T., Choi, W., and Bahnemann, D. W., “Environmental Applications of Semiconductor Photocatalysis,” Chem. Rev., 95(1), 69-96(1995) https://doi.org/10.1021/cr00033a004
  3. Fujishima, A., Rao, T. N., and Tryk, D. A.,“ Titanium dioxide photocatalysis,”J. Photochem. Photobiol. C: Photochem. Rev., 1(1), 1-21(2000) https://doi.org/10.1016/S1389-5567(00)00002-2
  4. Yamashita, H., Ichihashi, Y., Takeuchi, M., Kishiguchi, S., and Anpo, M., “Characterization of metal ion-implanted titanium oxide photocatalysts operating under visible light irradiation,”J. Synchrotron Rad., 6, 451-452(1999) https://doi.org/10.1107/S0909049598017257
  5. Anpo, M., and Takeuchi, M. “Design and development of second-generation titanium oxide photocatalysts to better our environment-approaches in realizing the use of visible light,” Int. J. Photoenergy, 3(2), 89-94(2001) https://doi.org/10.1155/S1110662X01000101
  6. Borgarello, E., Kiwi, J., Gratzel, M., and Pelizzetti, E.,“ Visible light induced water cleavage in colloidal solutions of chromiumdoped titanium dioxide particles,”J. Am. Chem. Soc., 104(11), 2996-3002(1982) https://doi.org/10.1021/ja00375a010
  7. Zhao, W., Ma, W. H., Chen, C. C., Zhao, J. C., and Shuai, Z. G., “Efficient degradation of toxic organic pollutants with $Ni_{2}O_{3}/TiO_{2-x}B_{x}$ under visible irradiation,”J. Am. Chem. Soc., 126(15), 4782-4783(2004) https://doi.org/10.1021/ja0396753
  8. Ren, W. J., Ai, Z. H., Jia, F. L., Zhang, L. Z., Fan, X. X., and Zou, Z. G., “Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline $TiO_{2}$,”Appl. Catal. B: Environ., 69(3-4), 138-144(2007) https://doi.org/10.1016/j.apcatb.2006.06.015
  9. Yu, J. G., Zhou, M. H., Cheng, B., and Zhao, X. J.,“ Preparation, characterization and photocatalytic activity of in situ N,Scodoped $TiO_{2}$powders,”J. Mol. Catal. A: Chem., 246(1-2), 176-184(2006) https://doi.org/10.1016/j.molcata.2005.10.034
  10. Li, D., Haneda, H., Labhsetwar, N. K., Hishita, S., and Ohashi, N., 'Visible-light-driven photocatalysis on fluorine-doped $TiO_{2}$ powders by the creation of surface oxygen vacancies,' Chem. Phys. Lett., 401(4-6), 579-584(2005) https://doi.org/10.1016/j.cplett.2004.11.126
  11. Sato, S., “Photocatalytic activity of NOx-doped TiO2 in the visible light region,”Chem. Phys. Lett., 123(1-2), 126-128(1986) https://doi.org/10.1016/0009-2614(86)87026-9
  12. Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., and Taga, Y., “Visible-light photocatalysis in Nitrogen-doped titanium oxides,”Science, 293(5528), 269-271(2001) https://doi.org/10.1126/science.1061051
  13. Ihara, T., Miyoshi, M., Iriyama, Y., Matsumoto, O., and Sugihara, S., “Visible-light-active titanium oxide photocatalyst realized by an oxygen-deficient structure and by nitrogen doping,”Appl. Catal. B: Environ., 42(4), 403-409(2003) https://doi.org/10.1016/S0926-3373(02)00269-2
  14. Wang, Z. P., Cai, W. M., Hong, X. T., Zhao, X. L., Xu, F., and Cai, C. G., “Photocatalytic degradation of phenol in aqueous nitrogen-doped TiO2 suspensions with various light sources,” Appl. Catal. B: Environ., 57(3), 223-231(2005) https://doi.org/10.1016/j.apcatb.2004.11.008
  15. Mozia, S., Tomaszewska, M., Kosowaska, B., Grzmil, B., and Morawski, A. W.,“ Decomposition of nonionic surfactant on a nitrogen-doped photocatalyst under visible-light irradiation,” Appl. Catal. B: Environ., 55(3), 195-200(2005) https://doi.org/10.1016/j.apcatb.2004.09.019
  16. Lin, J., Lin, Y., Liu, P., Meziani, M. J., Allard, L. F., and Sun, Y., “Hot-Fluid Annealing for Crystalline Titanium Dioxide Nanoparticles in Stable Suspension,”J. Am. Chem. Soc., 124(38), 11514-11518(2002) https://doi.org/10.1021/ja0206341
  17. Harris, M. T., Brunson, R. R., and Byers, C. H.,“ The basecatalyzed hydrolysis and condensation reactions of dilute and concentrated TEOS solutions,”J. Non-Cryst. Solids, 121(1-3), 397-403(1990) https://doi.org/10.1016/0022-3093(90)90165-I
  18. Huo, Y., Bian, Z., Zhang, X., Jin, Y., Zhu, J., and Li, H., “Highly Active $TiO_{2-x}N_{x}$ Visible Photocatalyst Prepared by NDoping in $Et_{3}N$/EtOH Fluid under Supercritical Conditions,”J. Phys. Chem. C, 112(16), 6546-6550(2008) https://doi.org/10.1021/jp711966c
  19. Valentin, C. D., Finazzi, E., Pacchioni, G., Selloni, A., Livraghi, S., Paganini M. C., and Giamello, E., “N-doped $TiO_{2}$: theory and experiment,”Chem. Phys., 339(1-3), 44-56(2007) https://doi.org/10.1016/j.chemphys.2007.07.020
  20. Irie, H., Watanabe, Y., and Hashimoto, K., “Nitrogen- Concentration Dependence on Photocatalytic Activity of $TiO_{2-x}N_{x}$ Powders,”J. Phys. Chem. B, 107(23), 5483-5486(2003) https://doi.org/10.1021/jp030133h
  21. Stylidi, M., Kondarides, D. I., and Verykios, X. E., “Visible light-induced photocatalytic degradation of Acid Orange 7 in aqueous $TiO_{2}$,”Appl. Catal. B: Environ., 47(3), 189-201(2004) https://doi.org/10.1016/j.apcatb.2003.09.014