光催化分解水制氢.ppt

Areas where nanotechnolgy can contribute Organic Solar Cells Assembly of molecular clusters Photoinduced charge separation in donor-acceptor based molecular clusters Conversion of light energy into electricity Photocatalysis with Metal-Semiconductor Composites Electron storage in metal nanoparticles Fermi-level equilibration Particle size effect (Applications in hydrogen production) Direct bandgap excitation of the semiconductor results in electron-hole separation Photogenerated holes as well as hydroxyl radicals oxidize the organic contaminant at the TiO2 surface Electrons are scavenged by oxygen Semiconductor nanoparticles as photocatalysts hn O2 e t h t VB – + + – O2- Ar-Cl CO2+HCl CB X OH? OH- hn e t h t VB – + + – CB 2H2O+ O2 4OH- H2 2H+ 2H+ H2 Pt Hydrogen production is observed only in presence of a precious metal catalyst. It is important that we look into other metals as catalysts Semiconductor (e.g., TiO2) nanoparticles for hydrogen production What about gold and other noble metals? Hydrogen Evolution rates for various Photocatalysts (ml/hr) Pt/TiO2 7.7 Pd/TiO2 6.7 Rh/TiO2 2.8 Ru/TiO2 0.2 Sn/TiO2 0.2 Ni/TiO2 0.1 TiO2 0.1 Toshima, J. Phys. Chem. 1985, 89, 1902 Photocatalytic water splitting reactions TiO2 Pt h e 2H+ H2 4OH- 2H2O + O2 hn Role of nanogold in catalysis Size and support dependency of catalytic activity of gold clusters on titania, Haruta, et al Catal. Today, 1997, 36, 153 Structural and electronic properties of Au on TiO2(110), Yang, Z.X., R.Q. Wu, and D.W. Goodman, Phys. Rev. B, 2000, 6, 14066-14071. High-performance nanocatalysts for single-step hydrogenations. Thomas, J. M., Johnson, B. F. G., Raja, R., Sankar, G. and Midgley, P. A., Acc. Chem. Res., 2003, 36, 20-30. (Bimetallic nanoparticles (Ru6Pd6, Ru6Sn, Ru10Pt2, and Ru12Ag4) anchored within silica nanopores exhibit high activities) Catalysis with TiO2/gold nanocomposites. Effect of metal particle size on the Fermi level equilibration, Subramanian, V., E. Wolf,