Surface Modification of TiO2 by Phosphate:  Effect on Photocatalytic Activity and Mechanism Implication

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Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100080, China and Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, Illinois 62901
Cite this: J. Phys. Chem. C 2008, 112, 15, 5993–6001
Publication Date (Web):March 25, 2008
Copyright © 2008 American Chemical Society
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Phosphate modified TiO2 photocatalysts were prepared by phosphoric acid treatment before or after TiO2 crystallization. Substrates with different structures were chosen to explore the photocatalytic activity of as-modified TiO2 under UV irradiation. It was found that the effect of phosphate modification is definitely attributed to the surface-bound phosphate anion, and the modification by phosphate can affect both the rates and pathways of photocatalytic reactions, which are of great dependence on the structures and properties of substrates. The degradation of substrates (such as 4-chloropehenol, phenol, and rhodamine B) with weak adsorption on the pure TiO2 was markedly accelerated by phosphate modification, while substrates (such as dichloroacetic acid, alizarin red, and catechol) with strong adsorption exhibited a much lower degradation rate in the phosphate modified system. A much higher amount of hydroxyl radical was produced in phosphate modified system. All of the experimental results imply that phosphate modification largely accelerates the hydroxyl radical attack, but hinders the direct hole oxidation pathway. A common operating mechanism for the phosphate modification, which can be applicable to other inert anions, is also discussed from the viewpoint of an anion-induced negative electrostatic field in the surface layer of TiO2 and the hydrogen bond between modification anion and H2O molecule.

 Chinese Academy of Sciences.


 To whom correspondence should be addressed. Fax:  86-10-8261-6495. E-mail:  [email protected]

 Southern Illinois University.

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TGA curves; calculation formula for relative surface hydroxyl density; the FTIR spectra of P0.05-TiO2, P0.10-TiO2, P0.20-TiO2; the Ti 2p and O 1s XPS spectra and the corresponding difference spectra of O 1s; the degradation kinetic curves of various of substrates and the degradation rates of hydroquinone. This material is available free of charge via the Internet at

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