Bifunctionality of Rh3+ Modifier on TiO2 and Working Mechanism of Rh3+/TiO2 Photocatalyst under Irradiation of Visible Light

A rhodium(III) ion (Rh3+)-modified TiO2 (Rh3+/TiO2) photocatalyst, prepared by a simple adsorption method and exhibiting high levels of photocatalytic activity in degradation of organic compounds, was investigated by using X-ray absorption fine structure (XAFS) measurements, (photo)electrochemical measurements, double-beam photoacoustic (DB-PA) spectroscopic measurements, and photoluminescence measurements. Based on the results, the features of the Rh3+ modifier and the working mechanism of the Rh3+/TiO2 photocatalyst are discussed. XAFS measurements revealed that the Rh3+ species were highly dispersed and almost atomically isolated on TiO2. The (photo)electrochemical measurements, DB-PA spectroscopic measurements, and photoluminescence showed a unique bifunction of the Rh3+ modifier as a promoter for O2 reductions and an electron injector to the conduction band of TiO2 for response to visible light. The reasons for the Rh3+/TiO2 photocatalyst exhibiting higher levels of photocatalytic activity than those...

[1]  Shinichirou Takahashi,et al.  Reaction Mechanism of Cu(II)-Grafted Visible-Light Responsive TiO2 and WO3 Photocatalysts Studied by Means of ESR Spectroscopy and Chemiluminescence Photometry , 2011 .

[2]  T. Ikeda,et al.  Nickel(II) oxide surface-modified titanium(IV) dioxide as a visible-light-active photocatalyst. , 2011, Chemical communications.

[3]  H. Kominami,et al.  Photocatalytic mineralization of volatile organic compounds over commercial titanium(IV) oxide modified with rhodium(III) ion under visible light irradiation and correlation between physical properties and photocatalytic activity , 2011 .

[4]  H. Tada,et al.  Titanium(IV) dioxide surface-modified with iron oxide as a visible light photocatalyst. , 2011, Angewandte Chemie.

[5]  H. Tada,et al.  Visible-Light-Active Iron Oxide-Modified Anatase Titanium(IV) Dioxide , 2011 .

[6]  H. Kominami,et al.  Photocatalytic degradation of 2-propanol over metal-ion-loaded titanium(IV) oxide under visible light irradiation: Effect of physical properties of nano-crystalline titanium(IV) oxide , 2011 .

[7]  F. Luck A Review of Support Effects on the Activity and Selectivity of Hydrotreating Catalysts , 2010 .

[8]  K. Hashimoto,et al.  An Efficient Visible-Light-Sensitive Fe(III)-Grafted TiO2 Photocatalyst , 2010 .

[9]  H. Kominami,et al.  Photocatalytic Degradation of 2-Propanol under Irradiation of Visible Light by Nanocrystalline Titanium(IV) Oxide Modified with Rhodium Ion Using Adsorption Method , 2010 .

[10]  K. Hashimoto,et al.  Conduction band energy level control of titanium dioxide: toward an efficient visible-light-sensitive photocatalyst. , 2010, Journal of the American Chemical Society.

[11]  T. Yokoyama,et al.  Characterization of Cr(III)-grafted TiO2 for photocatalytic reaction under visible light , 2010 .

[12]  T. Yokoyama,et al.  Visible Light-Sensitive Cu(II)-Grafted TiO2 Photocatalysts: Activities and X-ray Absorption Fine Structure Analyses , 2009 .

[13]  F. Parrino,et al.  Visible light photocatalysis by a Titania–Rhodium(III) complex , 2009 .

[14]  T. Ohno,et al.  Exposed crystal surface-controlled TiO2 nanorods having rutile phase from TiCl3 under hydrothermal conditions , 2009 .

[15]  Toshiki Tsubota,et al.  Shape-Controlled Anatase Titanium(IV) Oxide Particles Prepared by Hydrothermal Treatment of Peroxo Titanic Acid in the Presence of Polyvinyl Alcohol , 2009 .

[16]  Toshiki Tsubota,et al.  Switching redox site of photocatalytic reaction on titanium(IV) oxide particles modified with transition-metal ion controlled by irradiation wavelength , 2008 .

[17]  Y. Nosaka,et al.  Selective Production of Superoxide Ions and Hydrogen Peroxide over Nitrogen- and Sulfur-Doped TiO2 Photocatalysts with Visible Light in Aqueous Suspension Systems , 2008 .

[18]  B. Ohtani,et al.  Pristine simple oxides as visible light driven photocatalysts: highly efficient decomposition of organic compounds over platinum-loaded tungsten oxide. , 2008, Journal of the American Chemical Society.

[19]  K. Hashimoto,et al.  Efficient visible light-sensitive photocatalysts: Grafting Cu(II) ions onto TiO2 and WO3 photocatalysts , 2008 .

[20]  B. Ohtani,et al.  Double-Beam Photoacoustic Spectroscopic Studies on Transient Absorption of Titanium(IV) Oxide Photocatalyst Powders , 2007 .

[21]  K. Asai,et al.  Preparation of S-doped TiO2 photocatalysts and their photocatalytic activities under visible light , 2004 .

[22]  B. Ohtani,et al.  Discrimination of the active crystalline phases in anatase–rutile mixed titanium(IV) oxide photocatalysts through action spectrum analyses , 2002 .

[23]  Y. Nosaka,et al.  Properties of O2.- and OH. formed in TiO2 aqueous suspensions by photocatalytic reaction and the influence of H2O2 and some ions , 2002 .

[24]  R. Asahi,et al.  Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides , 2001, Science.

[25]  T. Inui,et al.  Hydrolysis of Titanium Alkoxide in Organic Solvent at High Temperatures: A New Synthetic Method for Nanosized, Thermally Stable Titanium(IV) Oxide , 1999 .

[26]  D. Meissner,et al.  Modified, Amorphous Titania-A Hybrid Semiconductor for Detoxification and Current Generation by Visible Light. , 1998, Angewandte Chemie.

[27]  M. Anpo Photocatalysis on titanium oxide catalysts: Approaches in achieving highly efficient reactions and realizing the use of visible light , 1997 .

[28]  Y. Nosaka,et al.  Application of Chemiluminescent Probe to Monitoring Superoxide Radicals and Hydrogen Peroxide in TiO2 Photocatalysis , 1997 .

[29]  J. Rehr,et al.  Near-edge x-ray-absorption fine structure of Pb: A comparison of theory and experiment. , 1993, Physical review. B, Condensed matter.

[30]  Shinri Sato,et al.  Photocatalytic activity of NOx-doped TiO2 in the visible light region , 1986 .

[31]  S. Matsuda,et al.  Titanium oxide based catalysts - a review , 1983 .

[32]  I. P. Alimarin,et al.  Chloride complexes of rhodium (III) in aqueous solutions , 1969 .

[33]  B. Ohtani,et al.  Novel solvothermal synthesis of niobium(V) oxide powders and their photocatalytic activity in aqueous suspensions , 2001 .

[34]  A. Miyamoto,et al.  Promoting effect of TiO2 and Al2O3 supports on the activity of vanadium oxide catalyst for the oxidation of benzene measured in terms of the turnover frequency , 1980 .