Lattice‐S Regulation of CoOOH Spin State and Surface Microenvironment Enables High‐Activity, High‐Selectivity, Industrial‐Level Electrocatalytic Glycerol Upgrading

ABSTRACT Electrocatalytic upgrading of biomass‐derived glycerol into high value‐added formate presents significant energy and chemical application potential. Herein, an anion‐S modification strategy was employed to precisely modulate the electronic structure and surface chemistry of CoOOH, enabling highly efficient glycerol‐to‐formate (GOR) conversion. The resulting CoOOH‐S catalyst requires only 1.25 and 1.31 V (vs. RHE) to achieve 100 and 500 mA cm −2 , respectively. Moreover, it delivers a formate selectivity and Faradaic efficiency of 96% and 95% at 1.4 V, surpassing most systems reported so far. Notably, under flow‐electrolysis conditions, the CoOOH‐S achieves industrial‐level current densities of 1.0 and 1.5 A cm −2 at merely 2.14 and 2.27 V, and maintains stable operation for over 500 h at > 500 mA cm −2 . Such GOR activity can be attributed to the modification of S, which disrupts the original octahedral symmetry of CoOOH, induces elongation of the Co─O bond and lattice distortion, and promotes electron redistribution and the presence of unpaired electrons, thereby enhancing electron transport and intrinsic activity. Meanwhile, the lower electronegativity of S strengthens the cooperative adsorption of OH − and glycerol, accelerating dehydrogenation and formate dissociation. This study elucidates the synergistic role of anion doping in regulating proton deintercalation and substrate adsorption on Co‐based catalysts.