Selective Photocatalytic Activation of Ethanol C–H and O–H Bonds over Multi-Au@SiO₂/TiO₂: Role of Catalyst Surface Structure and Reaction Kinetics

The chemical bond diversity and flexible reactivity of biomass-derived ethanol make it a vital feedstock for the production of value-added chemicals but result in low conversion selectivity. Herein, composite catalysts comprising SiO2-coated single- or multiparticle Au cores hybridized with TiO2 nanoparticles (mono- or multi-Au@SiO2/TiO2, respectively) were fabricated via electrostatic self-assembly. The C–H and O–H bonds of ethanol were selectively activated (by SiO2 and TiO2, respectively) under irradiation to form CH3CH•(OH) or CH3CH2O• radicals, respectively. The formation and depletion kinetics of these radicals was analyzed by electron spin resonance to reveal marked differences between mono- and multi-Au@SiO2/TiO2. Consequently, the selectivity of these catalysts for 1,1-diethoxyethane after 6 h irradiation was determined as 81 and 99%, respectively, which was attributed to the more pronounced effect of localized surface plasmon resonance for multi-Au@SiO2/TiO2. Notably, only acetaldehyde was formed on a Au/TiO2 catalyst without a SiO2 shell. Fourier transform infrared (FTIR) spectroscopy indicated that the C–H adsorption of ethanol was enhanced in the case of multi-Au@SiO2/TiO2, while NH3 temperature-programmed desorption and pyridine adsorption FTIR spectroscopy revealed that multi-Au@SiO2/TiO2 exhibited enhanced surface acidity. Collectively, the results of experimental and theoretical analyses indicated that the adsorption of acetaldehyde on multi-Au@SiO2/TiO2 was stronger than that on Au/TiO2, which resulted in the oxidative coupling of ethanol to afford 1,1-diethoxyethane on the former and the dehydrogenation of ethanol to acetaldehyde on the latter.