Unravelling the Dynamic Modulation of Copper (Oxy)Hydroxides for Electrocatalytic Organic Nucleophile Oxidation
Abstract
Abstract Electrocatalytic nucleophile oxidation (NOR) is pivotal for renewable energy and sustainable synthesis, yet the ambiguous nature of active sites hinders catalyst design. Herein, we thoroughly investigate the dynamic activation of CuO under NOR using surface voltammetry, in situ Raman, and impedance spectroscopies. Direct voltametric and spectroscopic evidences reveal that the adsorbed hydroxyl‐bridged Cu δ+ ‐oxy species (μ 2 ‐OH‐Cu δ+ ‐oxy, 2 ≤ δ ≤ 3) are the catalytically active centers for the reaction. Experimental–theoretical synergy reveals that the dynamic μ 2 ‐OH‐Cu δ+ ‐oxy interacts with stabilized OH* to form a dual‐site, dictating the structure–activity relationship. This mechanism enables near‐quantitative conversion of 5‐hydroxymethylfurfural to 2,5‐furandicarboxylic acid (97.1% yield/Faradaic efficiency) with > 100 h stability. The mechanistic insights we obtained show broad applicability across various nucleophilic substrates, where substituent effects, carbon chain flexibility, and α‐hydrogen mobility govern reactivity variations. This study establishes dynamic active center engineering as a universal strategy for designing transition‐metal (oxy)hydroxide catalysts, bridging electrocatalysis and precision organic synthesis.
Article Details
Authors (10)
Ziyi Fan
Qianqian Yang
Wenjun Zhang
Huiming Wen
Kaiwei Meng
State Key Laboratory for Development and Utilization of Forest Food Resources Nanjing Forestry University Nanjing 210037 China
En Zhao
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Jiangsu Province Key Laboratory of Green Biomass-Based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Longpan Road 159, Nanjing 210037, People’s Republic of China
Lin Dong
Center for Infection Biology, School of Basic Medical Sciences, Tsinghua University
Haiyang Yuan
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
Hua Gui Yang
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
Zupeng Chen
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Jiangsu Province Key Laboratory of Green Biomass-Based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Longpan Road 159, Nanjing 210037, People’s Republic of China