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

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. © 2024 Wiley-VCH GmbH.