Co@NC Chainmail Nanowires for Thermo‐ and Electrocatalytic Oxidation of 2,5‐Bis(hydroxymethyl)furan to 2,5‐Furandicarboxylic Acid

2,5‐Furandicarboxylic acid (FDCA) has emerged as an important bio‐based furanic compound, which has broad application prospects in renewable energy and materials, especially in the preparation of polyethylene 2,5‐furandicarboxylate (PEF). While the conventional synthesis of FDCA involves oxidation of 5‐hydroxymethylfurfural (HMF) as a substitute, the thermal and chemical instability of HMF due to its aldehyde group poses challenges. A more favorable alternative is the utilization of 2,5‐bis(hydroxymethyl)furan (BHMF), a non‐aldehyde and more stable precursor. This study pioneeringly reports nitrogen‐doped‐carbon encapsulated cobalt (Co@NC) chainmail nanowires for the thermal and electrocatalytic oxidation of BHMF to FDCA. The Co@NC/NF achieved a 97.9% conversion of BHMF with a 93.3% yield of FDCA at 1.475 V vs. RHE, whereas thermal catalysis only obtained 14.9% FDCA yield after 10 hours. Kinetic studies indicated that the large electrochemically active surface area and excellent kinetic parameters contribute its superior electrochemical performance. Mechanistic analysis revealed that the migration of inner electrons to the exterior modified the electronic properties of the carbon layer, thereby facilitating the oxidation of BHMF. Furthermore, the in‐situ generation of high‐valent cobalt species markedly accelerated the BHMF oxidation. This research underscores the potential of carbon‐encapsulated metal chainmail catalysts in thermal and electrochemical biomass conversion.