Interfacial Bridge Bonds Induced Strong Electronic Coupling of Co@V‐WO_x Catalyst for Enhanced Concurrent Co‐Electrolysis Performance

Abstract The integration of the hydrogen evolution reaction (HER) with the glycerol oxidation reaction (GOR) presents a promising strategy for hydrogen production with high‐value chemicals. Herein, a strongly electronically coupled Co@V‐WO_x material is presented with an amorphous nanosheet morphology, synthesized via a one‐step electrodeposition method. Experimental and theoretical investigations reveal that V doping induces robust electronic interactions between Co and the V‐WO_x host through the formation of Co─O─V/W interfacial bridge bonds, enhancing electron transfer capability for superior activity. As a result, the Co@V‐WO_x catalyst achieves an exceptionally low potential of −102 mV and 1.32 V at 100 mA cm⁻², along with a remarkable Faradaic efficiency of 95.4% for formate production at 1.40 V. A two‐electrode electrolyzer based on Co@V‐WO_x demonstrates ≈100% Faradaic efficiency for hydrogen evolution, a Faradaic efficiency exceeding 92.8% and a production rate of 59.4 mg h⁻¹ cm⁻² for formate, as well as outstanding stability over 300 h at 100 mA cm⁻², surpassing those previously reported Co‐based electrocatalysts. The in situ spectroscopic analyses and theoretical simulations further confirm that Co@V‐WO_x facilitates superior reaction kinetics by promoting the formation of active species and key reaction intermediates while lowering reaction energy barriers for electrolysis.