Synergistic modulation of electronic structure and surface hydroxyl species in PtPdCuSnBi multi-principal element alloy nanoparticles promotes electrocatalytic ethylene glycol to glycolate conversion

Electrocatalytic ethylene glycol oxidation reaction (EGOR) is a sustainable technique for production of value-added C2 chemicals, but it suffers from the large dosage of noble metals and poor stability of electrocatalysts. Herein, we designed a PtPdCuSnBi multi-principal element alloy nanoparticles (PtPdCuSnBi MPEA NPs), the incorporation of Cu, Sn and Bi not only modulated electronic structure and coordination environment of Pt and Pd, but also enhanced the generation of active *OH ad species during EGOR, thus it exhibits superior EGOR performance with high mass activity ( 1 0 . 2 5 A m g − 1 N M ) and Faradaic efficiency of glycolate (∼95.1%) at 0.8 V vs. RHE, and enhanced catalytic stability. The in-situ electrochemical infrared reflection absorption spectroscopy (IRAS) results confirmed the C2 pathway and enhanced ability of EG-to-GA electroconversion on PtPdCuSnBi MPEA NPs. Further combined with the density functional theory (DFT) calculations, it is demonstrated that Pt and Pd exhibit significant electron-enrichment effect, and d -band center of Pt moves upward close to the Fermi level in MPEA structure, thus exhibiting a stronger adsorption of reaction intermediates to achieve a lower energy barrier of rate-determining step (*OCH 2 -CH 2 OH → *OHC-CH 2 OH). This study provides a new paradigm for rationally modulating the structure of Pt-group metals to fabricate low-cost electrocatalyts for electrocatalytic upgrading of EG and other small-molecule alcohols.