Exposure of Au Atom on Au(111) in Metal Nanoclusters for pH‐Universal Electrocatalysis

The control of surface and interface structures in nanocatalysts is a promising strategy for enhancing catalytic performance, but significant challenges persist in achieving precisely designed active sites or environments on the surface/interface of fully protected metal nanoclusters. In this study, we report the construction of an exposed Au atom on Au(111) and the formation of a unique surface/interface environment on the Au₅₂ cluster via a cyclopentanethiol-etching strategy. Theoretical calculations and in situ attenuated total reflection infrared adsorption spectroscopy reveal that the exposed Au atom facilitates CO₂ activation, while the tailored surface/interface environment promotes the accumulation of strongly hydrogen-bonded water, which can be validated by the molecular dynamic simulation, thus enhancing proton transfer and suppressing hydrogen evolution reaction (HER). Notably, the surface/interface-modified Au₅₂ cluster showcases high activity, selectivity, and durability across pH-universal (acidic, neutral, and alkaline) electrolytes, providing new insights for designing high-performance electrocatalysts at atomic level.