Efficient Glycerol Oxidation on PMo₁₂‐Encapsulated MOF‐74 Electrocatalyst Coupled With Hydrogen Evolution at Industrial‐Level Current Density

Abstract Hybrid water electrolysis, integrating thermodynamically favorable glycerol oxidation (GOR) with hydrogen evolution reaction (HER), offers an energy‐efficient route for H₂ and value‐added chemical production. However, designing high‐performance GOR electrocatalysts for industrial‐scale applications remains a significant challenge. Herein, a host‐guest metal–organic framework (MOF) heterogeneous electrocatalyst, encapsulating a Keggin‐type polyoxometalate (POM) cluster (H₃PMo₁₂O₄₀) within the Co‐based MOF‐74 (denoted as PMo₁₂@MOF‐74) for efficient GOR, is developed. Profiting from the electronic structure modulation induced by strong host‐guest interactions, PMo₁₂@MOF‐74 exhibits exceptional GOR activity, requiring only 1.25 V versus RHE to achieve the current density of 100 mA cm⁻², with a Faradaic efficiency (FE) of 92.48% and selectivity of 89.08% for formic acid (FA). When coupled with the cathodic MoC@CoO catalyst, the flow electrolyzer achieves impressive performance at an industrial‐level current density of 1 A cm⁻² at 2.15 V, with satisfactory stability for up to 24 h. In situ Raman analysis and theoretical calculations demonstrate that POM encapsulation facilitates the surface reconstruction to form CoOOH active species and lowers the energy barrier for the rate‐determining step (RDS), thereby enhancing the activity of MOF‐74 electrocatalyst for GOR. This work offers a new strategy for designing MOF‐based heterogeneous catalysts for co‐production of hydrogen and high‐value FA with low energy input.