Interphase electron redistribution induced by confined transformation in PtPdBiSn nanoplates for efficient ethanol oxidation electrocatalysis.

Noble metal-based core/shell catalysts show great promise for ethanol oxidation reaction (EOR) through regulated dehydrogenation or bond-breaking, yet their performance remains constrained by limited interphase electron interactions accessible through conventional structure-conserving modulation strategies. Herein, we report a strategy of confined heterostructural transformation within the core to enhance interphase electron interactions, electrochemically transforming ordered hexagonal close-packed (HCP)/ face-centered cubic (FCC) PtPdBiSn nanoplates into disordered hexagonal non-close-packed (H-nCP)/FCC heterostructured catalyst for efficient EOR. Advanced characterization and density functional theory (DFT) calculations reveal that the confined transformation induces interphase electron redistribution: electron transfer from core to shell. This effect reconfigures the electronic structure, optimizing intermediates' adsorption energetics and reaction energy barriers. This reconstructed catalyst exhibits the mass and specific activity of 28.17 A mg-1NM (noble metals) (18.4 × Pt/C) and 85.7 mA cm-2 (26.1 × Pt/C), retains 80.3% activity after 20,000 cycles, and demonstrates enhanced CO tolerance. This work transcends conventional Pt-based HCP/FCC heterostructure design by elucidating confined heterostructural transformation-induced interphase electron redistribution enhancement mechanisms, offering a potential strategy for developing efficient analogous catalysts.