Enhancing Plasmonic Hot Electron Energy on Ag Surface by Amine Coordination

Plasmonic catalysis has emerged as a promising approach to solar‐chemical energy conversion. Notably, hot carriers play a decisive role in plasmonic catalysis since only when their energy matches with the LUMO or HOMO energy of the reactant molecule, can the reaction be activated. However, the hot carrier energy depends on the intrinsic physicochemical properties of the plasmonic metal substrate and the interaction with incident light. Tuning the hot carrier energy is of great significance for plasmonic catalysis but remains challenging. Here, we demonstrate that the energy of hot electrons can be significantly elevated to an unprecedented level through the coordination of amines on Ag surface. The bonding of amines and Ag reduces the work function of nanoparticles, leading to the increase of hot electron energy by 0.4 eV. This enhancement of energy promotes the cleavage of C−X (X=Cl, F) bonds upon excitation by visible light. This study provides new insights for promoting plasmonic charge transfer and enhancing the photocatalytic performance of plasmon‐mediated systems. Surface coordination induces a substantial enhancement in plasmonic hot electron energy, thereby enabling the achievement of previously inaccessible visible‐light‐driven cleavage of C−X (X=F, Cl) bonds using individual plasmonic metal.