Atomically Dispersed Gold Nanoclusters and Single Atoms Coexisting Chiral Electrode for High‐Performance Enantioselective Electrosynthesis using H2o as Hydrogen Source

Abstract Developing chiral electrode catalysts for enantioselective electrosynthesis is a great challenge, as it requires catalysts that possess both high activity and enantioselectivity. Precise synthesis of nanoclusters and single atoms coexisting chiral catalysts provide a promising pathway for enhancing asymmetric catalytic performance. Herein, chiral electrode catalysts are fabricated comprising gold clusters ( R ‐Au C ) and single atoms ( R ‐Au S ) on graphene oxide ( R ‐Au C/S @GO) through an assembly‐irradiation strategy. Thereinto, the R ‐Aus is in situ generated from R ‐Au C under light irradiation. The monoatomization process can be precisely regulated by changing the wavelength of the light, resulting in four Au‐based chiral electrode ( R ‐Au@GO) catalysts with different ratios of nanoclusters and single atoms. These chiral electrodes are applied in the electrocatalytic enantioselective hydrogenation of methyl benzoylformate (MB) to chiral methyl mandelate ( S ‐MM), and the R ‐Au C/S‐2 @GO with ≈26% R ‐Au C and 74% R ‐Au S achieve the highest catalytic activity (35 µmol cm −2 h −1 productivity) and enantioselectivity [97% enantiomeric excess ( ee )]. Detailed experimental analysis and density functional theory calculations reveal that the R ‐Au S on GO promotes the in situ generation of H* species, and R ‐Au C mainly drives the enantioselective conversion of MB by transferring the H* species to the carbonyl group of MB, ultimately yielding chiral S ‐MM.