One step synthesis and characterization of copper doped sulfated titania and its enhanced photocatalytic activity in visible light by degradation of methyl orange

doi:10.1016/j.cjche.2015.11.026

摘要/Abstract

摘要： This paper reports on the synthesis of copper doped sulfated titania nano-crystalline powders with varying (2.0%-10.0%, by mass) by single step sol gel method. The synthesized photo catalyst has been characterized by employing various techniques like X-ray Diffraction (XRD), Ultraviolet-Visible Diffuse Reflection Spectroscopy (UV-Vis DRS), X-ray Photoelectron Spectroscopy (XPS), Scanning ElectronMicroscopy (SEM), Energy Dispersive Spectrometry (EDS), Fourier Transform Infrared Spectroscopic Studies (FT-IR), and Transmission Electron Microscopy (TEM). Fromthe XRD and TEMresults, all the sampleswere reported in anatase phasewith reduction in particle size in the range of 7 to 12 nm. SEMindicated the change inmorphology of the particles. The presence of copper in titania lattice was evidenced by XPS. From UV-Vis DRS and FT-IR studies indicated that prominent absorption shift is observed towards visible region (red shift), the entry of Cu²⁺ into TiO₂ lattice as a substitutional dopant and SO₄^2- ions were covalently bonded with Ti⁴⁺ on the surface of the copper doped titania respectively.
The photocatalytic activity studies were investigated by consideringmethyl orange (MO) as dye pollutant in the presence of the visible light. The effect of various parameters like effect of dosage of the catalyst, dopant concentration, pH of the solution, and concentration of the dye was studied in detail.

关键词: Copper doped sulfated TiO₂, Sol-gel method, Photocatalysis, Methyl orange

Abstract: This paper reports on the synthesis of copper doped sulfated titania nano-crystalline powders with varying (2.0%-10.0%, by mass) by single step sol gel method. The synthesized photo catalyst has been characterized by employing various techniques like X-ray Diffraction (XRD), Ultraviolet-Visible Diffuse Reflection Spectroscopy (UV-Vis DRS), X-ray Photoelectron Spectroscopy (XPS), Scanning ElectronMicroscopy (SEM), Energy Dispersive Spectrometry (EDS), Fourier Transform Infrared Spectroscopic Studies (FT-IR), and Transmission Electron Microscopy (TEM). Fromthe XRD and TEMresults, all the sampleswere reported in anatase phasewith reduction in particle size in the range of 7 to 12 nm. SEMindicated the change inmorphology of the particles. The presence of copper in titania lattice was evidenced by XPS. From UV-Vis DRS and FT-IR studies indicated that prominent absorption shift is observed towards visible region (red shift), the entry of Cu²⁺ into TiO₂ lattice as a substitutional dopant and SO₄^2- ions were covalently bonded with Ti⁴⁺ on the surface of the copper doped titania respectively.
The photocatalytic activity studies were investigated by consideringmethyl orange (MO) as dye pollutant in the presence of the visible light. The effect of various parameters like effect of dosage of the catalyst, dopant concentration, pH of the solution, and concentration of the dye was studied in detail.

Key words: Copper doped sulfated TiO₂, Sol-gel method, Photocatalysis, Methyl orange

Radha Devi Chekuri, Siva Rao Tirukkovalluri. One step synthesis and characterization of copper doped sulfated titania and its enhanced photocatalytic activity in visible light by degradation of methyl orange[J]. Chinese Journal of Chemical Engineering, 2016, 24(4): 475-483.

参考文献

[1] R.J. Reid, Soc. Dyers Colour. 112(1996) 103-105.

[2] H. Zollinger (Ed.), Color Chemistry-Synthesis, Properties and Applications of Organic Dyes and Pigments, 2nd revised ed.VCH pubs, New York 1991, pp. 3144-3149.

[3] A. Francony, C. Petrier, Ultrason. Sonochem. 3(1996) S77-S82.

[4] P. Theron, P. Pichat, C. Petrier, C. Guillard, Water Sci. Technol. 44(2001) 263-270.

[5] C. Pulgarian, J. Kiwi, Chimia 50(1996) 50-55.

[6] J. Engweiler, J. Harf, A. Baiker, WOx/TiO₂ catalysts prepared by grafting of tungsten alkoxides,morphological properties and catalytic behavior in the selective reduction of NO by NH₃, J. Catal. 159(1996) 259-269.

[7] V. Brezova, A. Blazkova, L. Karpinsky, J. Groskova, B. Havlinova, V. Jorik, M. Eeppen, J. Photochem. Photobiol. A Chem. 109(1997) 177-183.

[8] H. Irie, Y.Watanabe, K. Hashimoto, Carbon-doped anatase TiO₂ powders as a visiblelight sentisive photocatalyst, Chem. Lett. 32(2003) 772-773.

[9] X. Liu, Z. Liu, J. Zheng, X. Yan, D. Chen, S. Li, W. Chu, Characteristics of N-doped TiO₂ nanotube arrays by N₂-plasma for visible light driven photocatalysis, J. Alloys Compd. 509(2011) 9970-9976.

[10] Y. Zhao, X. Qiu, C. Burda, The effects of sintering on the photocatalytic activity of Ndoped TiO₂ nanoparticles, Chem. Mater. 20(2008) 2629-2636.

[11] C. Cantau, T. Pigot, J.C. Dupin, S. Lacombe, N-doped TiO₂ by low temperature synthesis; stability, J. Photochem. Photobiol. A Chem. 216(2010) 201-208.

[12] X. Wu, D. Wu, Li, Optical investigation on sulphur doping effects in titanium dioxide nanoparticles, Appl. Phys. A: Mater. Sci. Process. 97(2009) 243-248.

[13] T. Ohno, M. Akiyoshi, T. Umebayashi, K. Asai, T. Mitsui, M. Matsumura, Appl. Catal. A Gen. 265(2004) 115-121.

[14] Y. Lu, L. Yu, H. Liu, Y. Feng, Preparation, characterization of P-doped TiO₂ nanoparticles and their excellent photocatalytic properties under the solar light irradiation, J. Alloys Compd. 488(2009) 314-319.

[15] D. Huang, S. Liao, S. Quan, L. Liu, Z. He, J. Wan, W. Zhou, Preparation of anatase F doped TiO₂ sol and its performance for photodegradation of formaldehyde, J. Mater. Sci. 42(2007) 8193-8202.

[16] W. Choi, A. Termin, M.R. Hoffmann, The role of metal ion dopants in quantum-sized TiO₂: Correlation between photoreactivity and charge carrier recombination dynamics, J. Phys. Chem. 98(51) (1994) 13669-13679.

[17] J.C.S. Wu, C.H. Chen, A visible-light response vanadium-doped titania nanocatalyst by sol-gel method, J. Photochem. Photobiol. A Chem. 163(3) (2004) 509-515.

[18] T. Umebayashi, T. Yamaki, H. Itoh, K. Asai, Band gap narrowing of titanium dioxide by sulfur doping, J. Appl. Phys. Lett. 81(2002) 454-456.

[19] T. Umebayashi, T. Yamaki, S. Tanala, K. Asai, Visible light-induced degradation of methylene blue on S-doped TiO₂, J. Chem. Lett. 32(4) (2003) 330-331.

[20] T. Umebayashi, T. Yamaki, S. Yamamoto, A. Miyashita, S. Tanala, T. Sumita, K. Asai, Sulfur-doping of rutile-titanium dioxide by ion implantation: Photocurrent spectroscopy and first-principles band calculation studies, J. Appl. Phys. 93(2003) 5156-5160.

[21] S.R. Yoganarasimhan, C.N.R. Rao, Trans. Faraday Soc. 58(1962) 1579-1589.

[22] M.A. Fox, M.T. Dulay, Chem. Rev. 93(1993) 341-357.

[23] C. Lettmann, K. Hildenbrand, H. Kisch, W. Macyk, W.F. Maier, Appl. Catal. B Environ. 32(2001) 215-227.

[24] I.H. Tseng, J.C.S. Wu, H.Y. Chou, Effects of sol-gel procedures on the photo catalysis of/Cu/TiO₂ in CO₂ photo reduction, J. Catal. 221(2004) 432-440.

[25] S. Xu, J. Ng, X. Zhang, H. Bai, D.D. Sun, Fabrication and comparison of highly efficient Cu incorporated TiO₂ photocatalyst for hydrogen generation from water, Hydrogen Energy 35(11) (2010) 5254-5261.

[26] H.J. Choi, M. Kang, Hydrogen production from methanol/water decomposition in a liquid photosystem using the anatase structure of Cu loaded TiO₂, J. Hydrogen Energy 32(2007) 3841-3848.

[27] M. Kitano, K. Funatsu, M. Matsuoka, M. Ueshima, M. Anpo, Preparation of nitrogensubstituted TiO₂ thin film photocatalysts by the radio frequency magnetron sputtering deposition method and their photocatalytic reactivity under visible light irradiation, J. Phys. Chem. B 110(2006) 25266-25272.

[28] T. Yamaguchi, Recent progress in solid superacid, Appl. Catal. 61(1990) 16-19.

[29] M. Hino, K. Arata, Polymerization of ethyl and methyl vinyl ethers catalyzed by iron oxide treated with sulfate ion synthesis of stereospecific, J. Chem. Lett. 7(1980) 963-966.

[30] Y.Wang, C. Chn, J. Luo, et al., Studies on the acidity, structures and crystalline phases of SO₄^2-/TiO₂, PO₄^3-/TiO₂, BO₃^3-/TiO₂ solid acids, Chinese, Struct. Chem. 18(3) (1990) 175-181.

[31] Y. Xu, L.Wang, Q. Zhang, S. Zheng, X. Li, C. Hung, Correlation between photo activity and photo physics of sulfated TiO₂ photo catalyst, J. Mater. Chem. Phys. 92(2005) 470-474.

[32] L.K. Noda, R.M. Aleida, L.F.D. Probst, N.S. Crocalves, Characterization of sulfated TiO₂ prepared by the sol-gel method and its catalytic activity in the n-hexane isomerization reaction, J. Mol. Catal. A Chem. 225(1) (2005) 39-46.

[33] G. Marci, Augugliarov, A. Bianco Prevot, E. Baiocchic, Garcia-Lopez, Loddov, L. Palmisano, M. Pramauroe Schiavella, Ann. Chim. Soc. Chim. Ital. 93(2003) 639-645.

[34] T. Wu, G. Liu, J. Zhao, H. Hidaka, N. Serpone, Phys. Chem. B 103(1991) 4862-4867.

[35] T. Wu, T. Lin, J. Zhao, H. Hidaka, N. Serpone, Environ. Sci. Technol. 33(1999) 1379-1387.