Ligand‐Hybridization Activates Lattice‐Hydroxyl‐Groups of NiCo(OH) x Nanowires for Efficient Electrosynthesis

Abstract Electrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high‐valence metal active sites toward 5‐hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value‐added chemical of 2,5‐furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand‐hybridized NiCo(OH) x nanowires (BZ‐NiCo(OH) x ) with ample electron‐deficient Ni/Co sites for HMFOR. The robust electron‐withdrawing capability of benzoic acid ligands in BZ‐NiCo(OH) x speeds up the electrochemical activation and dehydrogenation of lattice‐hydroxyl‐groups (M 2+ −O−H⇌M 3+ −O), boosting the formation of abundant electron‐deficient and high‐valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ‐NiCo(OH) x delivers a remarkable current density of 111.20 mA cm −2 at 1.4 V for HMFOR, exceeding that of NiCo(OH) x by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand‐hybridized strategy in this work introduces a novel perspective for designing high‐performance transition metal‐based electrocatalysts for biomass conversion.