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CeO修饰促进了在200 mA cm下由KA油氧化电合成己二酸的氧化动力学。

CeO Modification Promotes the Oxidation Kinetics for Adipic Acid Electrosynthesis from KA Oil Oxidation at 200 mA cm.

作者信息

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

机构信息

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, China.

Hebei Provincial Key Laboratory of Information Fusion and Intelligent Control, College of Engineering, Hebei Normal University, Shijiazhuang, 050024, China.

出版信息

Angew Chem Int Ed Engl. 2025 Mar 24;64(13):e202423432. doi: 10.1002/anie.202423432. Epub 2025 Jan 20.

Abstract

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, NiCoO/CeO is developed to enable the electrooxidation of cyclohexanol to AA with a 0.0992 mmol  h cm 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 CeO and NiCoO 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 CeO 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 by using KA oil as the anode feedstock at 2.5 A (200 mA cm), demonstrating promising potential.

摘要

水中环己醇/环己酮的电催化氧化为制备己二酸(AA)提供了一种很有前景的策略,己二酸是聚合物工业中的一种重要原料。然而,由于对反应机理了解不足,该过程受到动力学缓慢和法拉第效率(FE)有限的阻碍。在此,开发了NiCoO/CeO,以实现环己醇在较低电位下电氧化为己二酸,产率为0.0992 mmol h cm,法拉第效率为87%。机理研究表明,环己醇电氧化为己二酸是一个逐步氧化过程,包括环己醇脱氢为环己酮、生成2-羟基环己酮以及随后的C-C键断裂。理论计算表明,CeO与NiCoO之间的电子相互作用降低了环己酮氧化为2-羟基环己酮的能垒,并抑制了OH到O的步骤,从而实现了高产率和高法拉第效率的己二酸电合成。动力学分析进一步阐明了CeO对促进环己酮在电极表面吸附和活化的作用,从而加快了反应动力学。此外,构建了一个两电极流动反应器,以KA油为阳极原料,在2.5 A(200 mA cm)下生产72.1 mmol己二酸和10.4 L氢气,显示出广阔的应用前景。

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