Ultrafast Dynamics Simulations in the Plasmon-Induced Photocatalysis of Benzyl Alcohol by Nanoparticles

The solvent-free metal-catalyzed synthesis of benzaldehyde from benzyl alcohol requires high temperatures or pressures to achieve high reaction efficiencies, which can reduce the stability of the catalyst. To address this issue, utilizing solar energy to facilitate the photocatalytic conversion of benzyl alcohol into benzaldehyde via the plasmonic effects of metal nanoparticles under ambient conditions has emerged as a promising approach. However, the microscopic mechanism underlying the plasmon-induced photocatalytic conversion of benzyl alcohol remains unclear. In this work, we employ time-dependent density functional theory to investigate the ultrafast carrier dynamics during the plasmon-driven photocatalysis mediated by PdAu₃ nanoparticles, revealing the electron transfer process at the atomic scale during the photochemical reactions. Our findings indicate that the reaction is governed by multiple charge transfer mechanisms, with indirect charge transfer driven by hot carriers within the metal being predominant. Direct charge transfer between the metal and the adsorbed molecule, as well as within the adsorbed molecule, plays secondary roles. This study provides a detailed pathway for understanding the plasmon-driven photocatalytic conversion of benzyl alcohol to benzaldehyde and offers valuable insights into the design of catalysts for various organic syntheses under ambient conditions using light.