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

Abstract

The development of bifunctional electrocatalysts capable of integrating biomass-derived platform molecule oxidation with organic reduction offers a promising strategy for simultaneously enhancing energy efficiency and generating high-value chemicals. However, designing catalysts that exhibit both high activity and stability in integrated systems remains a significant challenge. Herein, we report a self-supported electrode composed of nitrogen-doped carbonized wood (NCW) supported NiCo nanosheets (NiCo_0.3/NCW) that enables the electrocatalytic 5-hydroxymethylfurfural oxidation to produce 2,5-furandicarboxylic acid (FDCA) and the nitrobenzene reduction to yield aniline in an integrated electrochemical cell. The NiCo_0.3/NCW electrode achieves the production of FDCA and aniline at a low cell voltage of 1.7 V, with ∼99% anodic and ∼92% cathodic Faradaic efficiencies, respectively. Experimental characterizations disclose that the hierarchical porous NCW architecture promotes the dispersion of active sites, while nitrogen doping strengthens metal-support interactions. In-situ spectroscopic experiments combined with density functional theory (DFT) calculations reveal that cobalt incorporation tunes the electronic structure of nickel, thus optimizing substrate and intermediate adsorption, and lowering energy barriers. These effects ultimately enhance the performance of the natural wood-derived catalyst in integrated biomass valorization and selective organic electrosynthesis.