Hierarchically Structured CuNiP/CuO_x‐V_P Nanoarrays Construction by Heteroatom Doping Boosting Glycerol Valorization at Industrial‐Level Current Density

Abstract Electrocatalytic valorization of glycerol to formate is considered to be a promising sustainable approach; however, it holds great challenges to increase catalyst activity and deliver market‐demanded chemicals with high Faradaic efficiency (FE) and selectivity under industrial‐level current density. Herein, hierarchically structured phosphorus vacancy‐enriched nickel phosphide porous nanoarrays by copper doping, denoted as CuNiP/CuO_x‐V_P, are constructed via a facile glycol‐mediated solvothermal approach. The CuNiP/CuO_x‐V_P yields an industry‐level 1 A cm⁻² at the ultralow potential of 1.75 V, while showing notable FE (96.94%) and selectivity (96.76%) to formate over a wide range of potentials. Impressively, a two‐electrode electrolyzer linked to H₂ evolution possesses exceptional activity that merely requires a cell voltage of 1.45 V to deliver 40 mA cm⁻², exhibiting a high FE (97.53%) for formate production and surpassing the vast majority of previously reported precious metal electrocatalysts. Microscopic and electrochemical characterizations manifest that the CuNiP/CuO_x‐V_P composed of porous NiP nanosheets attached to aggregated CuO_x particles featuring superaerophobic‐hydrophilic morphology enables increased active sites, favorable electronic redistribution, and thus boosted electrocatalytic performance. This study demonstrates an effective nanoarrays electrode for catalyst discovery, going from facile catalyst synthesis to structure‐activity relationship and subsequently developing more highly active electrocatalysts for energy‐saving coproduction of valuable chemicals.