Gao, Y.Tang, C.Zheng, Y.2025-09-182025-09-182025Journal of Energy Chemistry, 2025; 105:439-4452095-49562095-4956https://hdl.handle.net/2440/1474215-Hydroxymethylfurfural (HMF), derived from biomass, is a promising sustainable resource that can be converted into valuable chemical compounds. One such compound, 2,5-dihydroxymethylfuran (DHMF), produced through the electrocatalytic hydrogenation of HMF, is widely used in industrial polymer manufacturing. However, the hydrogenation of high-concentration HMF remains challenging due to the tendency for undesirable dimerization. Acknowledging the critical role of adsorbed hydrogen (H*) in HMF hydrogenation, a series of transition metal-doped dual-cubic Cu electrocatalysts (M-Cu, where M = Mo, Pd, Pt, Au, and Ag) were synthesized to systematically investigate the effect of varying H* reactivity on HMF hydrogenation. A pronounced correlation between DHMF selectivity and H* coverage was observed. Increasing H* coverage can enhance the selectivity for DHMF and prevent undesired dimerization of adsorbed HMF molecules. While elevated H* coverage enhanced DHMF selectivity, excessive coverage adversely impacted Faradaic efficiency due to competing hydrogen evolution reaction. This underscores the critical importance of finely tuning H* coverage. The optimal electrocatalyst, achieved by fine-tuning the doping amount of Pt on Cu, demonstrated a Faradaic efficiency of over 90% for DHMF in high-concentration HMF at −0.3 V, marking the highest record reported to date.en© 2025 The Authors. Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences.This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).Biomass; 5-Hydroxymethylfurfural; Electrocatalytic synthesis; HydrogenationJournal article10.1016/j.jechem.2025.02.010733427Gao, Y. [0000-0003-4617-8595]Tang, C. [0000-0002-5167-1192]Zheng, Y. [0000-0002-2411-8041]