Adsorption, Desorption, and Sensitization of Low-Index Anatase and Rutile Surfaces by the Ruthenium Complex Dye N3

Single-crystal anatase(101), (001) and rutile(100), (001) surfaces with atomically flat terraces were prepared and their structure verified with atomic force microscopy. A ruthenium complex dye, cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylate) ru-thenium(II) (usually known as N3) was used to sensitize these surfaces. The N3 coverage dependence of the incident photon to current efficiencies (IPCE) was measured for all four surfaces. IPCE values were much higher on anatase(101) and rutile(100) than on the other two surfaces. The kinetics of N3 adsorption was also studied on the four surfaces. The adsorption kinetics for a slow adsorption step could be fit with a Langmuir kinetic model. The differences in the adsorption of N3 and the IPCE values are discussed based on the structure of the N3 and the geometry and reactivity of the binding sites on the four surfaces.

[1]  Petter Persson,et al.  Calculated structural and electronic interactions of the ruthenium dye N3 with a titanium dioxide nanocrystal. , 2005, The journal of physical chemistry. B.

[2]  B. Parkinson,et al.  Dye sensitization of the anatase (101) crystal surface by a series of dicarboxylated thiacyanine dyes. , 2005, Journal of the American Chemical Society.

[3]  H. Koinuma,et al.  Crystal-face dependences of surface band edges and hole reactivity, revealed by preparation of essentially atomically smooth and stable (110) and (100) n-TiO(2) (rutile) surfaces. , 2005, The journal of physical chemistry. B.

[4]  Y. Nakato,et al.  Crystal-face and illumination intensity dependences of the quantum efficiency of photoelectrochemical etching, in relation to those of water photooxidation, at n-TiO2 (rutile) semiconductor electrodes , 2003 .

[5]  David R. Klug,et al.  Electron injection kinetics for the nanocrystalline TiO2 films sensitised with the dye (Bu4N)2Ru(dcbpyH)2(NCS)2 , 2002 .

[6]  B. Parkinson,et al.  Dye Sensitization of Natural Anatase Crystals with a Ruthenium-Based Dye , 2002 .

[7]  Anders Hagfeldt,et al.  Nanostructured ZnO electrodes for dye-sensitized solar cell applications , 2002 .

[8]  Y. Nakato,et al.  Selective Formation of Nanoholes with (100)-Face Walls by Photoetching of n-TiO2 (Rutile) Electrodes, Accompanied by Increases in Water-Oxidation Photocurrent , 2000 .

[9]  N. Harrison,et al.  The physical and electronic structure of the rutile (001) surface , 2000 .

[10]  B. Parkinson,et al.  The Adsorption Behavior of a Ruthenium‐Based Sensitizing Dye to Nanocrystalline TiO2 Coverage Effects on the External and Internal Sensitization Quantum Yields , 1999 .

[11]  A. J. Frank,et al.  Dye-Sensitized TiO2 Solar Cells: Structural and Photoelectrochemical Characterization of Nanocrystalline Electrodes Formed from the Hydrolysis of TiCl4 , 1999 .

[12]  Takeshi Miki,et al.  Dye-sensitization of n-TiO2 single-crystal electrodes with vapor-deposited oxometal phthalocyanines , 1999 .

[13]  John B. Asbury,et al.  Femtosecond IR Study of Excited-State Relaxation and Electron-Injection Dynamics of Ru(dcbpy)2(NCS)2 in Solution and on Nanocrystalline TiO2 and Al2O3 Thin Films , 1999 .

[14]  Valery Shklover,et al.  Structure of Organic/Inorganic Interface in Assembled Materials Comprising Molecular Components. Crystal Structure of the Sensitizer Bis[(4,4‘-carboxy-2,2‘-bipyridine)(thiocyanato)]ruthenium(II) , 1998 .

[15]  T. Miki,et al.  Scanning Probe Microscopic Characterization of Surface-Modified n-TiO2 Single-Crystal Electrodes , 1998 .

[16]  Ladislav Kavan,et al.  ELECTROCHEMICAL AND PHOTOELECTROCHEMICAL INVESTIGATION OF SINGLE-CRYSTAL ANATASE , 1996 .

[17]  A. Fujishima,et al.  Dye-sensitizing effect of TiOPc thin film on n-TiO2 (001) surface , 1996 .

[18]  Mohammad Khaja Nazeeruddin,et al.  Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes , 1993 .

[19]  P. Salvador,et al.  Catalytic role of lattice defects in the photoassisted oxidation of water at (001) n-titanium(IV) oxide rutile , 1992 .

[20]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[21]  M. Ryan,et al.  Internal reflection flash photolysis study of the photochemistry of eosin at titania semiconductor electrodes , 1989 .

[22]  M. Takata,et al.  Dye Sensitization and Surface Structures of Semiconductor Electrodes , 1980 .

[23]  L. Singh,et al.  Effect of the Ligand Structure on the Efficiency of Electron Injection from Excited Ru−Phenanthroline Complexes to Nanocrystalline TiO2 Films , 2002 .

[24]  G. Spoto,et al.  The morphology of TiO2 microcrystals and their adsorptive properties towards CO: a HRTEM and FTIR study , 1990 .