Simultaneous Electrocatalytic Oxidation and Hydrogenation of Biomass‐Derived Aldehydes on Single‐Atom Ru Catalysts

Abstract Simultaneous electrocatalytic oxidation (ECO) and hydrogenation (ECH) of biomass‐derived aldehydes offers a promising strategy for high‐value chemical production at both sides in a single electrolytic system. Herein, single‐atom Ru is anchored on Co(OH) 2 (Ru SAs/Co(OH) 2 ) to enable efficient ECO and ECH of 5‐hydroxymethylfurfural (HMF) yielding 2,5‐furandicarboxylic acid (FDCA) and 2,5‐dihydroxymethylfuran (DHMF) as target products. Comparative studies with pristine Co(OH) 2 reveal that Ru─N 4 sites enhance d‐p orbital hybridization, thereby strengthening HMF adsorption, reducing the activation energy of C═O bond, and improving the stability of Co active sites, as confirmed by theory and experiments. Thus, the yield of FDCA and DHMF over the Ru SAs/Co(OH) 2 electrode increases by 23.4% and 24.2% in comparison with its counterpart. In a symmetrical flow‐cell reactor equipped with Ru SAs/Co(OH) 2 catalyst, a remarkable combined yield of 177.7% (FDCA 92.3% + DHMF 85.4%) with perfect conversion of HMF is achieved within 6 h, and the high efficiency is stable over 240 h. The durability of this symmetrical system surpasses most reported systems (<50 h). Furthermore, the revenue of $5812.4 per FDCA ton is estimated for this symmetrical system, demonstrating enormous potential for industrial applications. This coupling work establishes a one‐stone‐two‐birds paradigm for biomass refinery using single‐atom catalysts.