The surface-structure sensitivity of dioxygen activation in the anatase-photocatalyzed oxidation reaction.

The reaction pathways by which oxygen is incorporated into the substrate in the photocatalytic oxidation of terephthalic acid (TPTA) are vastly different on {001} and {101} facets of an anatase single crystal. This was established by controlling the percentage of {101} and {001} facets, isotopically tracing the origins of the hydroxy group, and studying dioxygen consumption and variance in the concentration of hydroxylation intermediate.

[1]  W. Jenks,et al.  Photocatalytic Degradation of 4-Chlorophenol. 1. The Hydroquinone Pathway , 1999 .

[2]  A. Fujishima,et al.  TiO2 photocatalysis and related surface phenomena , 2008 .

[3]  Chuncheng Chen,et al.  An unexplored O2-involved pathway for the decarboxylation of saturated carboxylic acids by TiO2 photocatalysis: an isotopic probe study. , 2010, Chemistry.

[4]  A. Manivannan,et al.  Shape-enhanced photocatalytic activity of single-crystalline anatase TiO(2) (101) nanobelts. , 2010, Journal of the American Chemical Society.

[5]  Akira Fujishima,et al.  Titanium dioxide photocatalysis , 2000 .

[6]  Eric R. Waclawik,et al.  An efficient photocatalyst structure: TiO(2)(B) nanofibers with a shell of anatase nanocrystals. , 2009, Journal of the American Chemical Society.

[7]  G. Palmisano,et al.  Photocatalysis: a promising route for 21st century organic chemistry. , 2007, Chemical communications.

[8]  A. Selloni,et al.  Structure and Reactivity of Water Layers on Defect-Free and Defective Anatase TiO2(101) Surfaces , 2004 .

[9]  A. Fujishima,et al.  Generation and Deactivation Processes of Superoxide Formed on TiO2 Film Illuminated by Very Weak UV Light in Air or Water , 2000 .

[10]  P Hu,et al.  Identifying an O2 supply pathway in CO oxidation on Au/TiO2(110): a density functional theory study on the intrinsic role of water. , 2006, Journal of the American Chemical Society.

[11]  Jin Zou,et al.  Anatase TiO2 single crystals with a large percentage of reactive facets , 2008, Nature.

[12]  G. Dey Significant roles of oxygen and unbound •OH radical in phenol formation during photo-catalytic degradation of benzene on TiO2 suspension in aqueous system , 2009 .

[13]  A. Fujishima,et al.  Detection of active oxidative species in TiO2 photocatalysis using the fluorescence technique , 2000 .

[14]  Michio Matsumura,et al.  Determination of oxygen sources for oxidation of benzene on TiO2 photocatalysts in aqueous solutions containing molecular oxygen. , 2010, Journal of the American Chemical Society.

[15]  T. Tachikawa,et al.  Evidence for crystal-face-dependent TiO2 photocatalysis from single-molecule imaging and kinetic analysis. , 2011, Journal of the American Chemical Society.

[16]  Annabella Selloni,et al.  Structure and Energetics of Water Adsorbed at TiO2 Anatase (101) and (001) Surfaces , 1998 .

[17]  Anders Sandell,et al.  Water Dissociation on Single Crystalline Anatase TiO2(001) Studied by Photoelectron Spectroscopy , 2008 .

[18]  U. Diebold,et al.  Influence of Subsurface Defects on the Surface Reactivity of TiO2: Water on Anatase (101) , 2010 .

[19]  A. Selloni,et al.  O2 interaction and reactivity on a model hydroxylated rutile(110) surface. , 2005, The journal of physical chemistry. B.

[20]  Chuncheng Chen,et al.  Selective formation of imines by aerobic photocatalytic oxidation of amines on TiO2. , 2011, Angewandte Chemie.

[21]  Annabella Selloni,et al.  Structure and energetics of stoichiometric TiO 2 anatase surfaces , 2001 .

[22]  Renald Schaub,et al.  Oxygen-Mediated Diffusion of Oxygen Vacancies on the TiO2(110) Surface , 2002, Science.

[23]  Chuncheng Chen,et al.  Visible-light-induced aerobic oxidation of alcohols in a coupled photocatalytic system of dye-sensitized TiO2 and TEMPO. , 2008, Angewandte Chemie.

[24]  Ling Zang,et al.  Oxygen atom transfer in the photocatalytic oxidation of alcohols by TiO2: oxygen isotope studies. , 2009, Angewandte Chemie.

[25]  Zhi-Pan Liu,et al.  Mechanism and activity of photocatalytic oxygen evolution on titania anatase in aqueous surroundings. , 2010, Journal of the American Chemical Society.

[26]  Sean C. Smith,et al.  Solvothermal synthesis and photoreactivity of anatase TiO(2) nanosheets with dominant {001} facets. , 2009, Journal of the American Chemical Society.

[27]  Y. Tateyama,et al.  Interface Water on TiO2 Anatase (101) and (001) Surfaces: First-Principles Study with TiO2 Slabs Dipped in Bulk Water , 2010 .

[28]  G. Palmisano,et al.  Nanostructured rutile TiO2 for selective photocatalytic oxidation of aromatic alcohols to aldehydes in water. , 2008, Journal of the American Chemical Society.

[29]  T. Tachikawa,et al.  Design of a highly sensitive fluorescent probe for interfacial electron transfer on a TiO2 surface. , 2010, Angewandte Chemie.

[30]  C. Peden,et al.  Insights into Photoexcited Electron Scavenging Processes on TiO2 Obtained from Studies of the Reaction of O2 with OH Groups Adsorbed at Electronic Defects on TiO2 (110) , 2003 .

[31]  Jian Pan,et al.  On the true photoreactivity order of {001}, {010}, and {101} facets of anatase TiO2 crystals. , 2011, Angewandte Chemie.

[32]  O. Dulub,et al.  Local ordering and electronic signatures of submonolayer water on anatase TiO2(101). , 2009, Nature materials.