Bi‐Modulated Oxygen Vacancies for Enhanced Biomass‐Derived Glycerol Upgrading‐Assisted Hydrogen Evolution

ABSTRACT Electrocatalytic oxidation of biomass‐derived glycerol into valuable formic acid, assisting with hydrogen evolution, affords a promising scheme for biomass valorization and energy‐efficient hydrogen production, but designing highly active and selective electrocatalysts still maintains an enormous challenge. Hence, we present a transition‐metal bismuth‐modulated CuCoO x nanosheet array (BiCuCoO x ) grown on nickel foam (NF), which achieves a current density (300 mA cm −2 ) at a low potential of 1.36 V (vs. RHE), and delivers a preeminent formic acid Faradaic efficiency (FE) of 97.63%. Characterization results and density functional theory (DFT) calculations reveal that incorporating Bi not only induces abundant oxygen vacancies and modulates the local electronic structure to facilitate the electrochemical transformation process, but also enhances adsorption capacity for glycerol and OH − , accelerates the generation of surface CoOOH active species, and promotes the rapid consumption of glycerol through spontaneous chemical conversion, endowing high catalytic performance. Moreover, the two‐electrode GOR‐assisted hydrogen evolution exhibits a 315 mV reduction in the cell voltage at 100 mA cm −2 in comparison with conventional electrolysis of water. This work presents a viable design principle for assembling multi‐transition‐metal‐based oxide electrocatalysts that selectively cleave C─C bonds in glycerol into formic acid while simultaneously driving hydrogen evolution with low energy input.