Computational Criteria for Hydrogen Evolution Activity on Ligand-Protected Au₂₅-Based Nanoclusters

The hydrogen evolution reaction (HER) is a critical in addressing climate change; however, it requires catalysts to be generated on an industrial scale. Nanomaterials offer several advantages over conventional HER catalysts, including the possibility of atomic precision tailoring intrinsic activity. Ligand-protected metal clusters, such as thiolate-protected MAu24(SR)18 (where M Au, Cu, Pd), are particular interest not only they electrocatalytically active toward HER, but charge state and composition can precisely tuned. Here, we present comprehensive computational study examining how dopants affect catalytic activity [MAu24(SCH3)18]q Volmer step HER. Assuming adsorbed atom key intermediate, then, according Sabatier principle, H adsorption energy should nearly thermoneutral for ideal catalyst. Our results show that energies alone insufficient criterion identify promising material; experimentally relevant redox potentials, corresponding catalyst’s states, kinetic barriers also considered. Notably, this work explains relative (M = Pd) clusters reported by Kumar et al. (Nanoscale 2020, 12, 9969). validate more thorough approach includes potential understand screen nanoclusters.