Noble-metal-free TiO(2)photocatalysis for selective C & xe001;C reduction of alpha,beta-enones by CF3SO3H modification

The highly selective C & xe001;C reduction of alpha,beta-enones was realized by CF3SO3H-modifying noble-metal-free TiO(2)photocatalysis. Selectivity for C & xe001;C over C & xe001;O reduction was dramatically reversed from fair (similar to 42% without CF3SO3H-modifying) to excellent (>99%) upon only 6 mol% CF3SO3H loading without any noble-metal additive. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and(13)C-nuclear magnetic resonance (NMR) demonstrated that CF3SO3H modification results in the alpha,beta-enone polar C & xe001;O bond sitting away from rather than near to the active sites of polar TiO(2)catalysts.