Theoretical investigation of hydroamination of alkenes with aqueous ammonia by Pt/TiO2 photocatalyst

Abstract Precious-metal-supported TiO2 photocatalysts were shown to selectively synthesize primary amines. We attempted to elucidate the mechanism of this catalytic reaction via Density Functional Theory (DFT) calculations. Amino radicals are first formed at the hole-generated lattice oxygen on the surface of TiO2 and react with the substrate to form primary amine radicals. Finally, we successfully demonstrated that this primary amine radical reacts with hydrogen atoms on the catalyst surface to form an anti-Markovnikov final product.