Preparation of Cr-doped TiO2 thin film by sonochemical/CVD method and its visible light photocatalytic activity for degradation of paraoxon


1 Department of Semiconductors, Materials and Energy Research Center (MERC)

2 Ceramic Division, MERC


In this work, nanostructured TiO2 and Cr-doped TiO2 thin films were deposited on glass substrate through sonochemical-chemical vapor deposition (CVD) method. The resulting thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible absorption spectroscopy, and photoluminescence spectroscopy techniques. The TiO2 thin film has nanocubic morphology and the Cr-doped TiO2 thin film contains nanostructures with irregular shapes in its structures which these nanostructures themselves are composed from nanorods. Presence of Cr ions in the structure of TiO2 resulted in a decrease in the band gap energy of TiO2 and also in the reduction of photogenerated electron-hole recombination rate. The visible light photocatalytic activity of the prepared thin films were also investigated for degradation of paraoxon pesticide. According to the obtained results, the Cr-doped TiO2 thin film has higher photocatalytic activity than undoped TiO2 thin film. Moreover, in comparison with the undoped TiO2 thin film, the Cr-doped TiO2 thin film has higher stability.


Main Subjects

1. Chong, M.N., Jin, B., Chow, C.W., Saint, C., "Recent developments in photocatalytic water treatment technology: a review", Water Research, Vol. 44, No. 10, (2010), 2997-3027.
2. Chen, X., Mao, S.S., "Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications", Chemical Reviews, Vol. 107, No. 7, (2007), 2891-2959.
3. Devi, L.G., Kavitha, R., "A review on non metal ion doped titania for the photocatalytic degradation of organic pollutants under UV/solar light: role of photogenerated charge carrier dynamics in enhancing the activity", Applied Catalysis B: Environmental, Vol. 140, No. 1, (2013), 559-587.
4. Esfandiari, S., Honarvar Nazari, H., Nemati, A., Kargar Razi, M., Baghshahi, S., "Characterization of Structural, Optical and Hydrophilicity properties of TiO2 Nano-Powder Synthesized by Sol-Gel Method", Advanced Ceramics Progress, Vol. 2, No. 2, (2016), 1-6.
5. Landmann, M., Rauls, E., Schmidt, W., "The electronic structure and optical response of rutile, anatase and brookite TiO2", Journal of Physics: Condensed Matter, Vol. 24, No. 19, (2012), 195503.
6. Bhethanabotla, V.C., Russell, D.R., Kuhn, J.N., "Assessment of mechanisms for enhanced performance of Yb/Er/titania photocatalysts for organic degradation: Role of rare earth elements in the titania phase", Applied Catalysis B: Environmental, Vol. 202, No. 1, (2017), 156-164.
7. Khan, M.M., Ansari, S.A., Pradhan, D., Ansari, M.O., Lee, J., Cho, M.H., "Band gap engineered TiO2 nanoparticles for visible light induced photoelectrochemical and photocatalytic studies", Journal of Materials Chemistry A, Vol. 2, No. 3, (2014), 637- 644.
8. Bian, Z., Tachikawa, T., Zhang, P., Fujitsuka, M., Majima, T., "Au/TiO2 superstructure-based plasmonic photocatalysts exhibiting efficient charge separation and unprecedented activity", Journal of the American Chemical Society, Vol. 136, No. 1, (2013), 458-465.
9. Chen, J., Qiu, F., Xu, W., Cao, S., Zhu, H., "Recent progress in enhancing photocatalytic efficiency of TiO2-based materials", Applied Catalysis A: General, Vol. 495, No. 1, (2015), 131- 140.
10. Zuo, F., Bozhilov, K., Dillon, R.J., Wang, L., Smith, P., Zhao, X., Bardeen, C., Feng, P., "Active Facets on Titanium (III)‐ Doped TiO2: An Effective Strategy to Improve the Visible‐ Light Photocatalytic Activity", Angewandte Chemie, Vol. 124, No. 25, (2012), 6327-6330.
11. Roose, B., Pathak, S., Steiner, U., "Doping of TiO2 for sensitized solar cells", Chemical Society Reviews, Vol. 44, No. 22, (2015), 8326-8349.
12. Zhang, X., Zuo, G., Lu, X., Tang, C., Cao, S., Yu, M., "Anatase TiO2 sheet-assisted synthesis of Ti3+ self-doped mixed phase TiO2 sheet with superior visible-light photocatalytic performance: roles of anatase TiO2 sheet", Journal of Colloid and Interface Science, Vol. 490, No. 1,(2017), 774-782.
13. Song, J., Wang, X., Bu, Y., Wang, X., Zhang, J., Huang, J., Ma, R., Zhao, J., "Photocatalytic enhancement of floating photocatalyst: Layer-by-layer hybrid carbonized chitosan and Fe-N-codoped TiO2 on fly ash cenospheres", Applied Surface Science, Vol. 391, No. 1, (2017), 236-250.
14. Keihan, A.H., Hosseinzadeh, R., Farhadian, M., Kooshki, H., Hosseinzadeh, G., "Solvothermal preparation of Ag nanoparticle and graphene co-loaded TiO2 for the photocatalytic degradation of paraoxon pesticide under visible light irradiation", RSC Advances, Vol. 6, No. 87, (2016), 83673- 83687.
15. Sun, W.-T., Yu, Y., Pan, H.-Y., Gao, X.-F., Chen, Q., Peng, L.- M., "CdS quantum dots sensitized TiO2 nanotube-array photoelectrodes", Journal of the American Chemical Society, Vol. 130, No. 4, (2008), 1124-1125.
16. Schneider, J., Matsuoka, M., Takeuchi, M., Zhang, J., Horiuchi, Y., Anpo, M., Bahnemann, D.W., "Understanding TiO2 photocatalysis: mechanisms and materials", Chemical Reviews, Vol. 114, No. 19, (2014), 9919-9986.
17. Peng, Y.-H., Huang, G.-F., Huang, W.-Q., "Visible-light absorption and photocatalytic activity of Cr-doped TiO2 nanocrystal films", Advanced Powder Technology, Vol. 23, No. 1, (2012), 8-12.
18. Tian, B., Li, C., Zhang, J., "One-step preparation, characterization and visible-light photocatalytic activity of Crdoped TiO2 with anatase and rutile bicrystalline phases", Chemical Engineering Journal, Vol. 191, No. 1, (2012), 402- 409.
19. Ould‐Chikh, S., Proux, O., Afanasiev, P., Khrouz, L., Hedhili, M.N., Anjum, D.H., Harb, M., Geantet, C., Basset, J.M., Puzenat, E., "Photocatalysis with Chromium‐Doped TiO2: Bulk and Surface Doping", ChemSusChem, Vol. 7, No. 5, (2014), 1361-1371.
20. Li, X., Guo, Z., He, T., "The doping mechanism of Cr into TiO2 and its influence on the photocatalytic performance", Physical Chemistry Chemical Physics, Vol. 15, No. 46, (2013), 20037- 20045.
21. Bsiri, N., Zrir, M., Bardaoui, A., Bouaїcha, M., "Morphological, structural and ellipsometric investigations of Cr doped TiO2 thin films prepared by sol–gel and spin coating", Ceramics International, Vol. 42, No. 9, (2016), 10599-10607.
22. Chan, M.-H., Ho, W.-Y., Wang, D.-Y., Lu, F.-H., "Characterization of Cr-doped TiO2 thin films prepared by cathodic arc plasma deposition", Surface and Coatings Technology, Vol. 202, No. 4, (2007), 962-966.
23. Mendiola-Alvarez, S., Guzmán-Mar, J., Turnes-Palomino, G., Maya-Alejandro, F., Hernández-Ramírez, A., Hinojosa-Reyes, L., "UV and visible activation of Cr (III)-doped TiO2 catalyst prepared by a microwave-assisted sol–gel method during MCPA degradation", Environmental Science and Pollution Research, Vol. 24, No. 14, (2017), 12673-12682.
24. Jun, T.H., Lee, K.S., "Cr-doped TiO2 thin films deposited by RF-sputtering", Materials Letters, Vol. 64, No. 21, (2010), 2287-2289.
25. Ravidhas, C., Anitha, B., Raj, A.M.E., Ravichandran, K., Girisun, T.S., Mahalakshmi, K., Saravanakumar, K., Sanjeeviraja, C., "Effect of  itrogen doped titanium dioxide (NTiO2) thin films by jet nebulizer spray technique suitable for photoconductive study", Journal of Materials Science: Materials in Electronics, Vol. 26, No. 6, (2015), 3573-3582.26.
26. Osterwalder, J., Droubay, T., Kaspar, T., Williams, J., Wang, C.M., Chambers, S.A., "Growth of Cr-doped TiO2 films in the rutile and anatase structures by oxygen plasma assisted molecular beam epitaxy", Thin Solid Films, Vol. 484, No. 1, (2005), 289-298.
27. Lin, H.-y., Shih, C.-y., "Efficient one-pot microwave-assisted hydrothermal synthesis of M (M= Cr, Ni, Cu, Nb) and nitrogen co- doped TiO2 for hydrogen production by photocatalytic water splitting", Journal of Molecular Catalysis A: Chemical, Vol. 411, No. 1, (2016), 128-137.
28. Jovani, M., Domingo, M., Machado, T.R., Longo, E., Beltrán- Mir, H., Cordoncillo, E., "Pigments based on Cr and Sb doped TiO2 prepared by microemulsion-mediated solvothermal synthesis for inkjet printing on ceramics", Dyes and Pigments, Vol. 116, No. 1, (2015), 106-113.
29. Morosanu, C.E., Thin films by chemical vapour deposition, Elsevier, (2013).
30. Prasad, G., Ramacharyulu, P., Kumar, J.P., Srivastava, A., Singh, B., "Photocatalytic degradation of paraoxon-ethyl in aqueous solution using titania nanoparticulate film", Thin Solid Films, Vol. 520, No. 17, (2012), 5597-5601.
31. Mason, T.J., Lorimer, J.P., Applied sonochemistry: the uses of power ultrasound in chemistry and processing, Wiley-VCH Verlag GmbH Weinheim, (2002).
32. Cewers, G., Ultrasonic nebulizer, Google Patents, (2002).
33. Moussawi, R.N., Patra, D., "Synthesis of Au Nanorods through Prereduction with Curcumin: Preferential Enhancement of Au Nanorod Formation Prepared from CTAB-Capped over Citrate- Capped Au Seeds", The Journal of Physical Chemistry C, Vol. 119, No. 33, (2015), 19458-19468.
34. Tauc, J., "Absorption edge and internal electric fields in amorphous semiconductors", Materials Research Bulletin, Vol. 5, No. 8, (1970), 721-729.
35. Wu, G., Nishikawa, T., Ohtani, B., Chen, A., "Synthesis and characterization of carbon-doped TiO2 nanostructures with enhanced visible light response", Chemistry of Materials, Vol. 19, No. 18, (2007), 4530-4537.
36. Yang, K., Dai, Y., Huang, B., "Density Functional Characterization of the Electronic Structure and Visible‐Light Absorption of Cr‐Doped Anatase TiO2", ChemPhysChem, Vol. 10, No. 13, (2009), 2327-2333.
37. Wang, H., Lin, H., Long, Y., Ni, B., He, T., Zhang, S., Zhu, H., Wang, X., "Titanocene dichloride (Cp2 TiCl2) as a precursor for template-free fabrication of hollow TiO2 nanostructures with enhanced photocatalytic hydrogen production", Nanoscale, Vol. 9, No. 5, (2017), 2074-2081.
38. Liqiang, J., Yichun, Q., Baiqi, W., Shudan, L., Baojiang, J., Libin, Y., Wei, F., Honggang, F., Jiazhong, S., "Review of photoluminescence performance of nano-sized semiconductor materials and its relationships with photocatalytic activity", Solar Energy Materials and Solar Cells, Vol. 90, No. 12, (2006), 1773-1787.