Manipulating hydrogenation pathways enables economically viable electrocatalytic aldehyde- to- alcohol valorization

• 成果类型: Article
• 署名作者: Yao, Ze-Cheng; Chai, Jing; Tang, Tang; Ding, Liang; Jiang, Zhe; Fu, Jiaju; Chang, Xiaoxia; Xu, Bingjun; Zhang, Liang; Hu, Jin-Song; Wan, Li-Jun
• 署名单位: Chinese Academy of Sciences; Institute of Chemistry, CAS; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Tsinghua University; Peking University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-15064
• DOI: 10.1073/pnas.2423542122
• 发表日期: 2025-02-25
• 关键词: metal-support interactions; in-situ; conversion; mechanism; EVOLUTION; catalyst; water

摘要

Electrocatalytic reduction (ECR) of furfural represents a sustainable route for biomass 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 rate of 19.1 +/- 0.4 mol h-1 m-2 and a Faradaic efficiency of 97 +/- 1% at an economically efficient route for biofeedstock valorization with enhanced techno- economic feasibility.