复旦大学龚鸣团队报道了电催化生产己二酸，铜促进环己醇的氧化和C-C裂解。相关研究成果发表在2022年10月19日出版的《德国应用化学》。

己二酸是聚合物工业的中心平台分子。通过替代热化学路线的电重整技术，其生产指向了一种更可持续的工艺。

该文中，研究人员发现将Cu²⁺被引入氢氧化镍晶格显著提高了环己醇电催化氧化为己二酸盐的产率（84%）和选择性（87%）。这种Cu促进效应可以作为探针，结合产物分析、稳态动力学和原位光谱来研究其机理，其中包括首先两个电子氧化成环己酮，然后在二酮形成之前的早期阶段连续羟基化和C-C裂解。

Cu²⁺的中心作用是削弱NiOOH和表面吸附的O中心自由基之间的相互作用，这有助于随后的C-C裂解。该研究实现了将KA油电重整为己二酸盐和纯H₂的高效双电极系统。

附：英文原文

Title: Electrifying Adipic Acid Production: Copper-Promoted Oxidation and C-C Cleavage of Cyclohexanol

Author: Ran Wang, Yikun Kang, Jianxiang Wu, Tao Jiang, Yongjie Wang, Limin Gu, Yefei Li, Xuejing Yang, Zhipan Liu, Ming Gong

Issue&Volume: 2022-10-19

Abstract: Adipic acid is a central platform molecule for the polymer industry. Its production via the alternative electro-reforming technology to the thermochemical route points to a more sustainable process. Herein, we discovered that the incorporation of Cu2+ into the Ni hydroxide lattices significantly improved the electrocatalytic oxidation of cyclohexanol into adipate with a high yield (84%) and selectivity (87%). This Cu promotion effect could serve as a probe to combine with product analysis, steady-state kinetics and in situ spectroscopy to investigate the mechanism, which involves a first two-electron oxidation into cyclohexanone and then consecutive hydroxylation and C-C cleavage at early stages before the dione formation. The central role of Cu2+ is to weaken the interaction between the NiOOH and surface-adsorbed O-centered radical that facilitates the subsequent C-C cleavage. This enables a highly efficient two-electrode system of electro-reforming KA oil into adipate and pure H2.

DOI: 10.1002/anie.202214977

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202214977