CeO2 Modification Promotes the Oxidation Kinetics for Adipic Acid Electrosynthesis from KA Oil Oxidation at 200 mA cm<SUP>-2</SUP>

作     者：Guo, Shuoshuo Wang, Changhong Li, Huizhi Li, Tieliang Liu, Cuibo Gao, Ying Zhao, Bo-Hang Zhang, Bin 

作者机构：Tianjin Univ Sch Sci Dept Chem Tianjin 300072 Peoples R China Hebei Normal Univ Coll Engn Hebei Prov Key Lab Informat Fus & Intelligent Cont Shijiazhuang 050024 Peoples R China Tianjin Univ Inst Mol Plus Tianjin 300072 Peoples R China 

出 版 物：《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》 (Angew. Chem. Int. Ed.)

年 卷 期：2025年第64卷第13期

页      面：e202423432页

核心收录：

学科分类：081704[工学-应用化学] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：National Key Research and Development Program of China National Natural Science Foundation of China 2023YFA1507400 

主　　题：Electrocatalysis Adipic acid KA Oil oxidation CeO2 modification Kinetic analysis 

摘      要：Electrocatalytic oxidation of cyclohexanol/cyclohexanone in water provides a promising strategy for obtaining adipic acid (AA), which is an essential feedstock in the polymer industry. However, this process is impeded by slow kinetics and limited Faradaic efficiency (FE) due to a poor understanding of the reaction mechanism. Herein, NiCo2O4/CeO2 is developed to enable the electrooxidation of cyclohexanol to AA with a 0.0992 mmol h(-1) cm(-2) yield rate and 87 % Faradaic efficiency at a lower potential. Mechanistic investigations demonstrate that cyclohexanol electrooxidation to AA is a gradual oxidation process involving the dehydrogenation of cyclohexanol to cyclohexanone, the generation of 2-hydroxy cyclohexanone, and subsequent C-C cleavage. Theoretical calculations reveal that electronic interactions between CeO2 and NiCo2O4 decrease the energy barrier of cyclohexanone oxidation to 2-hydroxy cyclohexanone and inhibit the *OH to *O step, leading to AA electrosynthesis with a high yield rate and FE. Kinetic analysis further elucidates the effect of CeO2 on promoting cyclohexanone adsorption and activation on the electrode surface, thus facilitating the reaction kinetics. Moreover, a two-electrode flow reactor is constructed to produce 72.1 mmol AA and 10.4 L H-2 by using KA oil as the anode feedstock at 2.5 A (200 mA cm(-2)), demonstrating promising potential.