Ligand‐Mediated Interfacial Hydrogen Bonding Networks in Metal Organic Frameworks for High‐Performance 5‐Hydroxymethylfurfural Electrooxidation

Abstract

ABSTRACT Inspired by the 3D microenvironment modulated precise and efficient catalytic reactions in nature enzyme systems, we designed a NiCo‐based catalyst with 3D modulated microenvironments for high‐performance 5‐hydroxymethylfurfural (HMF) oxidation reaction by constructing metal organic frameworks (MOFs) with different side groups (SH‐MOF‐NiCo, OH‐MOF‐NiCo, and MOF‐NiCo). Our research indicates that the ─SH group in the porous structure could weaken the hydrogen bonding connectivity, which enhances the adsorption of HMF * and OH * species to promote α‐C‐H/O‐H activation. The optimized SH‐MOF‐NiCo electrode achieves a HMFOR current density of 463 mA cm ‒2 at 1.40 V vs. RHE, 100% HMF conversion, and 100% 2,5‐Furandicarboxylic acid (FDCA) selectivity at 1.45 V vs. RHE. Furthermore, the catalyst demonstrated remarkable efficiency in anion exchange membrane (AEM) electrolyzers, achieving high efficiency for high‐purity FDCA and H 2 production at a high current density (361 mA cm ‒2 ) with a voltage of 2.0 V, while maintaining operational durability for 210 h and continuous FDCA production with a yield of 97%. Importantly, this strategy not only enables efficient hydrogen production and biomass upgrading but also expands the scope to other biomass‐derived chemicals and high‐value‐added waste plastic conversion.