Rational Design of Transition‐Metal‐Based Catalysts for the Electrochemical 5‐Hydroxymethylfurfural Reduction Reaction

Abstract The electrochemical reduction reaction (HMFRR) of 5‐hydroxymethylfurfural (HMF) has emerged as a promising avenue for the utilization and refinement of the biomass‐derived platform molecule HMF into high‐value chemicals, addressing energy sustainability challenges. Transition metal electrocatalysts (TMCs) have recently garnered attention as promising candidates for catalyzing HMFRR, capitalizing on the presence of vacant d orbitals and unpaired d electrons. TMCs play a pivotal role in facilitating the generation of intermediates through interactions with HMF, thereby lowering the activation energy of intricate reactions and significantly augmenting the catalytic reaction rate. In the absence of comprehensive and guiding reviews in this domain, this paper aims to comprehensively summarize the key advancements in the design of transition metal catalysts for HMFRR. It elucidates the mechanisms and pH dependency of various products generated during the electrochemical reduction of HMF, with a specific emphasis on the bond‐cleavage angle. Additionally, it offers a detailed introduction to typical in‐situ characterization techniques. Finally, the review explores engineering strategies and principles to enhance HMFRR activity using TMCs, particularly focusing on multiphase interface control, crystal face control, and defect engineering control. This review introduces novel concepts to guide the design of HMFRR electrocatalysts, especially TMCs, thus promoting advancements in biomass conversion.