What determines the superior performance of Ni‐Co catalysts in selective hydrogenation of 5‐hydroxymethylfurfural?

Abstract Biomass‐derived 5‐hydroxymethylfurfural (HMF) can be converted into high‐value chemicals via hydrogenation, but competing pathways due to reducible functionalities pose selectivity challenges. Herein, a series of biochar‐supported Ni‐Co catalysts with varied metal ratios were synthesized to probe their structure‐performance relationships for HMF hydrogenation. Extensive characterizations reveal that the optimized Ni/Co ratio induces the formation of a Ni‐Co alloy phase, rather than NiCo 2 O 4 spinel or segregated monometallic species. Experimental and theoretical calculations collectively demonstrate that this alloy provides balanced hydrogen activation and optimized electronic properties for both CO activation and H 2 dissociation, which selectively promotes aldehyde hydrogenation while suppressing both furan ring saturation and hydroxymethylation‐reduction. The equimolar Ni‐Co catalyst achieved complete HMF conversion with >96% 2,5‐bis(hydroxymethyl)furan (BHMF) yield under mild conditions (2 MPa H 2 , 80°C), outperforming most noble and non‐noble metal catalysts. It also exhibits excellent recyclability and stability, highlighting the potential of biochar‐based catalysts for sustainable biomass valorization.