Breaking Activity‐Stability Trade‐Off by Switching Reaction Pathway for Efficient Electrosynthesis of Glycerate at Industrial‐Scale Current Density

ABSTRACT The selective electrooxidation of biomass represents a sustainable solution for the synthesis of high‐valued chemicals, yet it remains challenging to balance activity, selectivity, and stability. Herein, we report the selective regulation of β‐NiCoOOH and γ‐NiCoOOH through the precise modulation of precursors, demonstrating β‐NiCoOOH as active catalyst exhibit excellent performance for the electrocatalytic valorization of glycerol to glycerate (GLA) with a remarkable selectivity of 78.44% and an industrial‐scale current density of 1 A cm −2 in an anion exchange membrane electrolyzer for continuous long‐term operation of 1080 h. We revealed that the electrooxidation of glycerol to C3 product is contingent on the generation of β‐NiCoOOH phase with Co 3+ species as the dominant active center while γ‐NiCoOOH phase with a large amount of Co 4+ sites is beneficial to the cleavage of C─C bond for C1 product. Mass spectrometry and density functional theory (DFT) calculations elucidate that β‐NiCoOOH featuring inert lattice oxygen modulates the electronic configuration of the key glyceraldehyde intermediate, which enhances the stability of C─C bond, suppresses undesired cleavage, and thereby promotes the selective electrosynthesis of GLA via the ∙OH‐assisted adsorbate evolution mechanism (AEM). This work provides a scalable strategy and offers deep insights into the phase‐dependent reaction mechanisms in electrocatalytic biomass upgrading.