Electrifying Adipic Acid Production: Copper‐Promoted Oxidation and C−C Cleavage of Cyclohexanol. Issue 50 (16th November 2022)

• Record Type: Journal Article
• Authors: Wang, Ran; Kang, Yikun; Wu, Jianxiang; Jiang, Tao; Wang, Yongjie; Gu, Limin; Li, Yefei; Yang, Xuejing; Liu, Zhipan; Gong, Ming
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 50(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-11-16
• Subjects: Adipic Acid -- C−C Cleavage -- Electrocatalysis -- Electroreforming -- Radical; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202214977
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Adipic acid is a central platform molecule for the polymer industry. Production of adipic acid with electroreforming technology is more sustainable compared to the thermochemical synthesis route. We discovered that incorporation of Cu 2+ into a Ni hydroxide lattice significantly improved the electrocatalytic oxidation of cyclohexanol into adipate with a high yield (84 %) and selectivity (87 %). This Cu promotion effect serves as a mechanistic probe that can be combined with product analysis, steady‐state kinetics, and in situ spectroscopy. A two‐electron oxidation into cyclohexanone first occurs, followed by consecutive hydroxylation and C−C cleavage before dione formation. The central role of Cu 2+ is to weaken the interaction between the NiOOH and surface‐adsorbed O‐centered radical that facilitates subsequent C−C cleavage. This enables a highly efficient two‐electrode system capable of electroreforming KA oil into adipate and pure H2 . Abstract : Efficient electrocatalytic oxidation of cyclohexanol into adipate was achieved by incorporating copper into a nickel hydroxide electrode. Cu 2+ plays a key role in weakening the interaction between the surface‐adsorbed O‐centered radical and the NiOOH surface, thereby facilitating C−C cleavage.