Inhibiting the Deep Reconstruction of Ni‐Based Interface by Coordination of Chalcogen Anions for Efficient and Stable Glycerol Electrooxidation

Abstract Recently, Ni‐based chalcogenides havedemonstrated remarkable activity and selectivity for alcohol electrooxidation, but the mechanisms remain debated. This study synthesizes Ni‐based electrodeswith different chalcogen anion coordination on nickel nanorod arrays (NiO x /Ni,NiS x /Ni, and NiSe x /Ni NRAs). NiSe x /Ni NRAsshowcases superior performance (Faradaic efficiency 92.9%) in glycerolelectrooxidation reaction (GOR). In situ spectroscopy reveals that NiSecoordination inhibits deep oxidative reconstruction of the Ni‐based interface, preventingNiOOH phase formation during GOR, enhancing activity and stability of NiSe x /NiNRAs. Conversely, NiS and NiO coordination lead to deep reconstruction with NiOOHphase formation, limiting GOR performance. Differently, during competingreaction of GOR, the oxygen evolution reaction (OER) leads to deepreconstruction of NiSex interface due to the instability of Ni‐Sebonds, inducing performance degradation and dissolution of Se components. Furthermechanism investigation elucidates that the rate‐determining step (RDS) ofGOR at the NiSe x interface involves oxidation of *C 2 H 3 O 3 intermediatesthrough H 2 O adsorption, favoring stable formate production.Contrarily, the RDS at the NiS x , NiO x , and NiOOHinterfaces predominantly focus on the decarboxylation of multi‐carbon intermediates, raisingenergy barriers and over‐oxidizing formate to CO 2 . These results providenew insights for designing Ni‐based non‐oxide catalysts forefficient and stable electrocatalytic oxidation.