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

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/CuOx‐VP, are constructed via a facile glycol‐mediated solvothermal approach. The CuNiP/CuOx‐VP 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/CuOx‐VP composed of porous NiP nanosheets attached to aggregated CuOx 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. The hierarchically structured porous CuNiP/CuOx‐VP electrode with enriched P vacancies and atomic‐level Cu doping is achieved by a facile glycol‐mediated solvothermal approach excluding complicated chemical reactions and post‐treatment steps. Such CuNiP/CuOx‐VP electrode exhibits considerable FE (96.94%) and selectivity (96.76%) for electrocatalytic glycerol upgrading to formate at large current density, outperforming most noble‐metal catalysts in electrocatalytic GOR.