Mechanism of photocatalytic degradation of dye MG by TiO2-film electrode with cathodic bias potential
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Abstract
Photoelectrocatalytic degradation of malachite green (MG) under visible light irradiation with TiO2-film electrode has been investigated to reveal the mechanism for TiO2 photocatalytic degradation of dyes. The supported TiO2 electrode was prepared in laboratory and detected by scanning electron micros-copy and X-ray diffractometry. We have examined the degradation kinetics, change in degradation rate of MG and photocurrent change with the bias potential, voltage-induced adsorption of dyes, accumu-lation of electrons in the TiO2 electrode, effect of various additives such as benzoquinone (BQ), and formation of active oxygen species by UV-visible spectroscopy, TOC and spin-trap ESR spectrometry. It was found that the dyes could controllably interact with TiO2 surface by external bias and charge of dyes. The cationic dye MG underwent efficient mineralization at negative bias under visible light irradiation, but N-dealkylation process predominated at positive bias under visible light irradiation. At negative bias of −0.4 V vs SCE, the O2·− and dye·+ were formed simultaneously at the electrode/electrolyte interface during degradation of cationic MG. Experimental results imply both the superoxide radical and the dye cationic radical are essential to the mineralization of the dyes under visible-light-induced photocatalytic conditions.
Keywords
TiO2 electrode photocatalysis MG mineralization mechanismPreview
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References
- 1.O’Regan B, Gratzel M. A low-cost, high-efficiency solar cell based on dye sensitized colloidal TiO2 films. Nature, 1991, 353: 737–740CrossRefGoogle Scholar
- 2.Chen C C, Lu C S, Chung Y C. Photocatalytic degradation of ethyl violet in aqueous solution mediated by TiO2 suspensions. J Photochem Photobiol A: Chem, 2006, 181: 120–125CrossRefGoogle Scholar
- 3.Zhao W, Chen C C, Ma W H, et al. Efficient photoinduced conversion of an azo dye on hexachloroplatinate(IV)-modified TiO2 surfaces under visible light irradiation: A photosensitization pathway. Chem Eur J, 2003, 9: 2–8CrossRefGoogle Scholar
- 4.Stylidi M, Kondarides D I, Verykios X E. Visible light-induced photocatalytic degradation of acid orange 7 in aqueous TiO2 suspensions. Appl Catal B: Environ, 2004, 47: 189–201CrossRefGoogle Scholar
- 5.Bauer C, Jacques P, Kalt A. Photooxidation of an azo dye induced by visible light incident on the surface of TiO2. J Photochem Photobiol A: Chem, 2001, 140: 87–92CrossRefGoogle Scholar
- 6.Nasr C, Vinodgopal K, Fisher L, et al. Environmental photochemistry on semiconductor surfaces. Visible light induced degradation of a textile diazo dye, naphthol blue black, on TiO2 nanoparticles. J Phys Chem, 1996, 100: 8436–8442CrossRefGoogle Scholar
- 7.Wu T X, Lin T, Zhao J C, et al. TiO2-assisted photodegradation of dyes. 9. Photooxidation of a squarylium cyanine dye in aqueous dispersions under visible light irradiation. Environ Sci Technol, 1999, 33: 1379–1387CrossRefGoogle Scholar
- 8.Liu G M, Zhao J C, Hidaka H. ESR spin-trapping detection of radical intermediates in the TiO2-assisted photo-oxidation of sulforhodamine B under visible irradiation. J Photochem Photobiol A: Chem, 2000, 133: 83–88CrossRefGoogle Scholar
- 9.Chen C C, Li X Z, Ma W H, et al. Effect of transition metal ions on the TiO2-assisted photodegradation of dyes under visible irradiation: A probe for the interfacial electron transfer process and reaction mechanism. J Phys Chem B, 2002, 106: 318–324CrossRefGoogle Scholar
- 10.Chen C C, Zhao W, Li J, et al. Formation and identification of intermediates in the visible-light-assisted photodegradation of sulforhodamine-B dye in aqueous TiO2 dispersion. Environ Sci Technol, 2002, 36: 3604–3611CrossRefGoogle Scholar
- 11.Chen C C, Zhao W, Lei P X, et al. Photosensitized degradation of dyes in polyoxometalate solutions versus TiO2 dispersions under visible-light irradiation: mechanistic implications. Chem Eur J, 2004, 10: 1956–1963CrossRefGoogle Scholar
- 12.Vinodgopal K, Hotchandani S, Kamat P V. Electrochemically assisted photocatalysis: titania particulate film electrodes for photocatalytic degradation of 4-chlorophenol. J Phys Chem, 1993, 97: 9040–9044CrossRefGoogle Scholar
- 13.Liu H, Leng W H, Wu H J, et al. Study of photoelectrocatalytic degradation of sulfosalicylic acid. (in Chinese) Chin J Catal, 2000, 21: 209–212Google Scholar
- 14.Zanoni M, Sene J, Anderson M A. Photoelectrocatalytic degradation of remazol brilliant orange 3R on titanium dioxide thin-film electrodes. J Photochem Photobiol A: Chem, 2003, 157: 55–63CrossRefGoogle Scholar
- 15.Li J Q, Li L P, Zheng L, et al. Photoelectrocatalytic degradation of rhodamine B using Ti/TiO2 electrode prepared by laser calcination method. Electrochim Acta, 2006, 51: 4942–4949CrossRefGoogle Scholar
- 16.Rothenberger G, Fitzmaurice D, Gratzel M. Spectroscopy of conduction band electrons in transparent metal oxide semiconductor films: optical determination of the flatband potential of colloidal titanium dioxide films. J Phys Chem, 1992, 96: 5983–5986CrossRefGoogle Scholar
- 17.O’Regan B, Gratzel M, Fitzmaurice D. Optical electrochemistry. 2. Real-time spectroscopy of conduction band electrons in a metal oxide semiconductor electrode. J Phys Chem, 1991, 95: 10525–10528CrossRefGoogle Scholar
- 18.Bader H, Sturzenegger V, Hoigne J. Photometric method for the determination of low concentrations of hydrogen peroxide by the peroxidase catalyzed oxidation of N,N-diethyl-p-phenylenediamine (DPD). Water Res, 1988, 22: 1109–1112CrossRefGoogle Scholar
- 19.Chen C C, Lu C S, Chung Y C, et al. UV light induced photodegradation of malachite green on TiO2 nanoparticles. J Hazard Mater, 2007, 141: 520–528CrossRefGoogle Scholar
- 20.Cao F, Oskam G, Searson P. Electrical and optical properties of porous nanocrystalline TiO2 films. J Phys Chem, 1995, 99: 11974–11980CrossRefGoogle Scholar
- 21.Maning L E, Kramer M K, Foote C S. Interception of O2 − by benzoquinone in cyanoaromatic-sensitized photooxygenations. Tetrahedron Lett, 1984, 25: 2523–2526CrossRefGoogle Scholar
- 22.Harbour J R, Hair M L. Detection of superoxide ions in nonaqueous media. Generation by photolysis of pigment dispersions. J Phys Chem, 1978, 82: 1397–1399CrossRefGoogle Scholar
- 23.Sawyer D T, Valentine J S. How super is superoxide. Acc Chem Res, 1981, 14: 393–400CrossRefGoogle Scholar
- 24.Espinal L, Suib S L, Rusling J F. Electrochemical catalysis of styrene epoxidation with films of MnO2 nanoparticles and H2O2. J Am Chem Soc, 2004, 126: 7676–7682CrossRefGoogle Scholar
- 25.Cermenati L, Pichat P, Guillard C, et al. Probing the TiO2 photocatalytic mechanism in water purification by use of quinoline photo-Fenton generated OH radicals and superoxide dismutase. J Phys Chem B, 1997, 101: 2650–2658CrossRefGoogle Scholar