Mechanism of photocatalytic water oxidation on small TiO₂ nanoparticles.

ABSTRACT: We present the first unconstrained nonadiabatic molecular dynamics (NAMD) simulations of photocatalytic water oxidation by small hydrated TiO₂ nanoparticles using Tully surface hopping and time-dependent density functional theory. The results indicate that ultrafast electron-proton transfer from physisorbed water to the photohole initiates the photo-oxidation on the S₁ potential energy surface. The new mechanism readily explains the observation of mobile hydroxyl radicals in recent experiments. Two key driving forces for the photo-oxidation reaction are identified: localization of the electron-hole pair and stabilization of the photohole by hydrogen bonding interaction. Our findings illustrate the scope of recent advances in NAMD methods and emphasize the importance o

SUBMITTER: Muuronen M 

PROVIDER: S-EPMC5407260 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature