Abstract
In this article, palladium modification and silver modification were used as examples to demonstrate the disinfection effects on microorganisms in aqueous environment of photocatalytic transition-metal-ion-modified nitrogen-doped titanium oxide (TiON/M) materials. Transition metal ion modification was applied to TiON to take advantage of the coupling between transition metal ion addition and TiON semiconductor matrix under visible light illumination. The coupling promotes the separation of electron and hole pairs produced by photon excitation, thus it could reduce the intrinsic charge carrier recombination from anion-doping, which largely limits the photoactivity of TiON under visible light illumination. Large enhancements on the hydroxyl radical production and the photocatalytic disinfection efficiency on microorganisms under visible light illumination were observed for TiON with both palladium and silver modifications. The superior photocatalytic performance under visible light illumination suggests that the transition metal ion modification is an effective approach to reduce the massive charge carrier recombination from anion-doping and to enhance the photocatalytic performance of anion-doped TiO2. The resulting photocatalytic materials have the potential for a wide range of environmental applications.
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RincóA.G. n, C. Pulgarin, N. Adler, P. Peringer Interaction between E. coli inactivation and DBP-precursors–dihydroxybenzene isomers–in the photocatalytic process of drinking-water disinfection with TiO2. J. Photochem. Photobiol., A 139, 233 (2001)
W.J. Cooper, E. Cadavid, M.G. Nickelsen, K.J. Lin, C.N. Kurucz, T.D. Waite Removing THMs from drinking water using high-energy electron-beam irradiation. J. Am. Water Works Assn. 85, 106 (1993)
Al-Bastaki: N.M. Performance of advanced methods for treatment of wastewater: UV/TiO2, RO and UF. Chem. Eng. Process. 43, 935 (2004)
A. Fujishima, K. Honda Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37 (1972)
N.S. Frank, A.J. Bard Heterogeneous photocatalytic oxidation of cyanide and sulfite in aqueous solutions at semiconductor powders. J. Phys. Chem. 81, 1484 (1977)
T. Matsunaga, T.R. Tomoda, T. Nakajima, H. Wake Photoelectrochemical sterilization of microbial cells by semiconductor powders. FEMS Microbiol. Lett. 29, 211 (1985)
M.A. Fox, M.T. Dulay Heterogeneous photocatalysis. Chem. Rev. 93, 341 (1993)
M.R. Hoffman, S.T. Martin, W. Choi, D.W. Bahnemann Environmental applications of semiconductor photocatalysis. Chem. Rev. 95, 69 (1995)
A. Hagfeldt, M. Graetzel Light-induced redox reactions in nanocrystalline systems. Chem. Rev. 95, 49 (1995)
H. Einaga, S. Futamura, T. Ibusuki Photocatalytic decomposition of benzene over TiO2 in a humidified airstream. Phys. Chem. Chem. Phys. 1, 4903 (1999)
A. Fujishima, T.N. Rao, D.A. Tryk Titanium dioxide photocatalysis. J. Photochem. Photobiol., A 1, 1 (2000)
M. Sokmen, F. Candan, Z. Sumer Disinfection of E. coli by the Ag–TiO2/UV system: Lipidperoxidation. J. Photochem. Photobiol., A 143, 241 (2001)
P.S.M. Dunlop, J.A. Byrne, N. Manga, B.R. Eggins The photocatalytic removal of bacterial pollutants from drinking water. J. Photochem. Photobiol., A 148, 355 (2002)
E.J. Wolfrum, J. Huang, D.M. Blake, P.C. Maness, Z. Huang, J. Fiest, W.A. Jacoby Photocatalytic oxidation of bacteria, bacterial and fungal spores, and model biofilm components to carbon dioxide on titanium dioxide-coated surfaces. Environ. Sci. Technol. 36, 3412 (2002)
J.C. Yu, W.K. Ho, J. Lin, K.Y. Yip, P.K. Wong Photocatalytic activity, antibacterial effect, and photoinduced hydrophilicity of TiO2 films coated on a stainless steel substrate. Environ. Sci. Technol. 37, 2296 (2003)
K. Sunada, T. Watanabe, K. Hashimoto Bactericidal activity of copper-deposited TiO2 thin film under weak UV light illumination. Environ. Sci. Technol. 37, 4785 (2003)
M. Cho, H.M. Chung, W.Y. Choi, J.Y. Yoon Different inactivation behaviors of MS-2 phage and Escherichia coli in TiO2 photocatalytic disinfection. Appl. Environ. Microbiol. 71, 270 (2005)
R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293, 269 (2001)
H. Irie, Y. Watanabe, K. Hashimoto Nitrogen-concentration dependence on photocatalytic activity of TiO2–xNx powders. J. Phys. Chem. B 107, 5483 (2003)
T. Lindgren, J.M. Mwabora, E. Avendaño, J. Jonsson, C.G. Granqvist, S.E. Lindquist Photoelectrochemical and optical properties of nitrogen doped titanium dioxide films prepared by reactive DC magnetron sputtering. J. Phys. Chem. B 107, 5709 (2003)
C. Burda, Y. Lou, X. Chen, A.C.S. Samia, J. Stout, J.L. Gole Enhanced nitrogen doping in TiO2 nanoparticles. Nano Lett. 3, 1049 (2003)
S.W. Yang, L. Gao New method to prepare nitrogen-doped titanium dioxide and its photocatalytic activities irradiated by visible light. J. Am. Ceram. Soc. 87, 1803 (2004)
G.R. Torres, T. Lindgren, J. Lu, C-G Granqvist, S.E. Lindquist Photoelectrochemical study of nitrogen-doped titanium dioxide for water oxidation. J. Phys. Chem. B 108, 5995 (2004)
R. Nakamura, T. Tanaka, Y. Nakato Mechanism for visible light responses in anodic photocurrents at N-doped TiO2 film electrodes. J. Phys. Chem. B 108, 10617 (2004)
S.U.M. Khan, Al-M. Shahry, W.B. Ingler Efficient photochemical water splitting by a chemically modified n-TiO2. Science 297, 2243 (2002)
S. Sakthivel, H. Kisch Daylight photocatalysis by carbon-modified titanium dioxide. Angew. Chem. Int. Ed. 42, 4908 (2003)
H. Irie, Y. Watanabe, K. Hashimoto Carbon-doped anatase TiO2 powders as a visible-light sensitive photocatalyst. Chem. Lett. 32, 772 (2003)
H. Wang, J.P. Lewis Effects of dopant states on photoactivity in carbon-doped TiO2. J. Phys. Condens. Matter 17, L209 (2005)
T. Umebayashi, T. Yamaki, H. Itoh, K. Asai Band gap narrowing of titanium dioxide by sulfur doping. Appl. Phys. Lett. 81, 454 (2002)
T. Umebayashi, T. Yamaki, S. Tanaka, K. Asai Visible light-induced degradation of methylene blue on S-doped TiO2. Chem. Lett. 32, 330 (2003)
T. Ohno, T. Mitsui, M. Matsumura Photocatalytic activity of S-doped TiO2 photocatalyst under visible light. Chem. Lett. 32, 364 (2003)
T. Yamamoto, F. Yamashita, I. Tanaka, F. Matsubara, A. Muramatsu Electronic states of sulfur doped TiO2 by first-principles calculations. Mater. Trans. 45, 1987 (2004)
J.C. Yu, W. Ho, J. Yu, H. Yip, P. Wong, J. Zhao Efficient visible-light-induced photocatalytic disinfection on sulfur-doped nanocrystalline titania. Environ. Sci. Technol. 39, 1175 (2005)
J.C. Yu, J.G. Yu, W.K. Ho, Z.T. Jiang, L.Z. Zhang Effects of F- doping on the photocatalytic activity and microstructures of nanocrystalline TiO2 powders. Chem. Mater. 14, 3808 (2002)
A.K. Ghosh, H.P. Maruska Photoelectrolysis of water in sunlight with sensitized semiconductor electrodes. J. Electrochem. Soc. 124, 1516 (1977)
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, 13669 (1994)
Anpo: M. Photocatalysis on titanium oxide catalysts: Approaches in achieving highly efficient reactions and realizing the use of visible light. Catal. Surv. Jpn. 1, 169 (1997)
V. Subramanian, E. Wolf, P.V. Kamat Semiconductor-metal composite nanostructures: To what extent do metal nanoparticles improve the photocatalytic activity of TiO2 films? J. Phys. Chem. B 105, 11439 (2001)
S.I. Shah, W. Li, C-P Huang, O. Jung, C. Ni Study of Nd3+, Pd2+, Pt4+, and Fe3+ dopant effect on photoreactivity of TiO2 nanoparticles. Proc. Natl. Acad. Sci. USA 99, 6482 (2002)
Q. Li, W. Liang, J.K. Shang Enhanced visible-light absorption from PdO nanoparticles in nitrogen-doped titanium oxide thin films. Appl. Phys. Lett. 90, 063109 (2007)
Q. Li, R. Xie, E.A. Mintz, J.K. Shang Enhanced visible-light photocatalytic degradation of humic acid by palladium oxide-sensitized nitrogen-doped titanium oxide. J. Am. Ceram. Soc. 90, 3863 (2007)
Q. Li, M.A. Page, B.J. Marinãs, J.K. Shang Treatment of coliphage MS2 with palladium-modified nitrogen-doped titanium oxide photocatalyst illuminated by visible light. Environ. Sci. Technol. 42, 6148 (2008)
Q. Li, Y.W. Li, P. Wu, R. Xie, J.K. Shang Palladium oxide nanoparticles on nitrogen-doped titanium oxide: Accelerated photocatalytic disinfection and post-illumination catalytic “memory.” Adv. Mater. 20, 3717 (2008)
P. Wu, R. Xie, J.K. Shang Enhanced visible-light photocatalytic disinfection of bacterial spores by palladium-modified nitrogen-doped titanium oxide. J. Am. Ceram. Soc. 91, 2957 (2008)
M.A. Daley, D. Tandon, J. Economy, E.J. Hippo Elucidating the porous structure of activated carbon fibers using direct and indirect methods. Carbon 34, 1191 (1996)
J. Tauc, R. Grigorovici, A. Vancu Optical properties and electronic structures of amorphous germanium. Phys. Status Solidi 15, 627 (1966)
R. Schuch, D. Nelson, V.A. Fischetti A bacteriolytic agent that detects and kills Bacillus anthracis. Nature 418, 884 (2002)
J.B. Cross, R.P. Currier, D.J. Torraco, L.A. Vanderberg, G.L. Wagner, P.D. Gladen Killing of Bacillus spores by aqueous dissolved oxygen, ascorbic acid, and copper ions. Appl. Environ. Microbiol. 69, 2245 (2003)
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Li, Q., Wu, P., Xie, R. et al. Enhanced photocatalytic disinfection of microorganisms by transition-metal-ion-modification of nitrogen-doped titanium oxide. Journal of Materials Research 25, 167–176 (2010). https://doi.org/10.1557/JMR.2010.0005
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DOI: https://doi.org/10.1557/JMR.2010.0005