Atomically Precise Supported Au15 Nanoclusters for Efficient and Selective Electrooxidation of Lignin-Derived Alcohols to Aromatic Ketones.

Selective electrooxidation of lignin-derived alcohols to value-added aromatic ketones enables sustainable biomass valorization, but remains limited by high overpotentials and competing C-C bond cleavage. Here, atomically precise Au15 nanoclusters supported on carbon black (Au15/CB) were prepared through a ligand-stabilized rapid pyrolysis strategy. Au-S-C anchoring preserves the discrete electronic structure of Au15 during immobilization. For 1-phenylethanol (1-PL) electrooxidation, Au15/CB delivers 10 mA cm-2 at 0.96 V versus RHE, representing a 650 mV potential decrease relative to the oxygen evolution reaction. It also achieves 94% conversion of 1-PL with 99% selectivity toward acetophenone and excellent cycling stability, outperforming its single-atom (Au1/CB) and nanoparticle (Au NPs/CB) counterparts. Mechanistic studies show that an upshifted d-band center facilitates Au-OHads formation and strengthens adsorption of key intermediates, thereby lowering the thermodynamic barrier while maintaining efficient product desorption. These findings highlight atomic precision as a strategy for selective biomass electro-upgrading.