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

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 H₂ 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.