Manipulating hydrogenation pathways enables economically viable electrocatalytic aldehyde-to-alcohol valorization
Ze‐Cheng Yao, Jing Chai, Tang Tang, Liang Ding, Zhe Jiang, Jiaju Fu, Xiaoxia Chang, Bingjun Xu, Liang Zhang, Jin‐Song Hu, Li‐Jun Wan
Abstract
Electrocatalytic reduction (ECR) of furfural represents a sustainable route for biomass valorization. Unfortunately, traditional Cu-catalyzed ECR suffers from diversified product distribution and industrial-incompatible production rates, mainly caused by the intricate mechanism−performance relationship. Here, we manipulate hydrogenation pathways on Cu by introducing ceria as an auxiliary component, which enables the mechanism switching from proton-coupled electron transfer to electrochemical hydrogen-atom transfer (HAT) and thus high-speed furfural-to-furfuryl alcohol electroconversion. Theoretical and kinetic analyses show that oxygen-vacancy-rich ceria delivers an efficient formation−diffusion−hydrogenation chain of H* by diminishing H* adsorption. Spectroscopic characterizations indicate that Cu/ceria interfacial perimeter enriches the local furfural, synergistically lowering the barrier of the rate-determining HAT step across the perimeter. Our Cu/ceria catalyst realizes high-rate HAT-dominated ECR for electrosynthesis of single-product furfuryl alcohol, achieving a high production rate of 19.1 ± 0.4 mol h −1 m −2 and a Faradaic efficiency of 97 ± 1% at an economically viable partial current density of over 0.1 A cm −2 . Our results demonstrate a highly efficient route for biofeedstock valorization with enhanced techno-economic feasibility.