Interface-engineered NiCo sites on natural wood-derived porous carbon substrate for efficient paired electrocatalysis

• • The NiCo 0.3/NCW electrode achieves ~99% anodic Faradaic efficiency for HMF oxidation to FDCA and ~92% cathodic Faradaic efficiency for nitrobenzene reduction to aniline at a low cell voltage of 1.7 V, demonstrating high selectivity and energy efficiency for paired electrocatalysis. • • The hierarchical porous structure of nitrogen-doped carbonized wood (NCW) promotes dispersion of NiCo nanosheets, while nitrogen doping strengthens metal-support interactions, leading to enhanced catalytic activity and stability. • • In-situ Raman spectroscopy and DFT calculations reveal that cobalt incorporation tunes the electronic structure of nickel, optimizing adsorption of substrates and intermediates and lowering energy barriers, which is critical for the observed performance enhancement. • • The integrated electrolysis system operates at a cell voltage of 1.7 V, significantly lower than conventional water splitting (typically >1.8 V), offering a more energy-efficient route for simultaneous production of FDCA and aniline, with potential for industrial scale-up.