Electrifying Adipic Acid Production: Copper-Promoted Oxidation and C-C Cleavage of Cyclohexanol.
Electrifying Adipic Acid Production: Copper-Promoted Oxidation and C-C Cleavage of Cyclohexanol.
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己二酸生产的通电：铜促进的氧化和环己醇的 C-C 裂解。
DOI：
10.1002/anie.202214977
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发表时间：
2022
影响因子：
--
通讯作者：
Ming Gong
中科院分区：
文献类型：
--
作者：
Ran Wang;Yikun Kang;Jianxiang Wu;Tao Jiang;Yongjie Wang;Limin Gu;Yefei Li;Xuejing Yang;Zhipan Liu;Ming Gong
己二酸是聚合物工业的核心平台分子。它的生产通过替代电重整技术的热化学路线指向一个更可持续的过程。在此，我们发现，引入到Ni氢氧化物晶格的Cu 2+显着提高环己醇的电催化氧化成己二酸的高产率（84%）和选择性（87%）。这种铜的促进作用可以作为一个探针，结合联合收割机与产品分析，稳态动力学和原位光谱研究的机制，这涉及到第一个双电子氧化成环己酮，然后连续的羟基化和C-C裂解在早期阶段之前的二酮形成。Cu ~（2+）的主要作用是削弱NiOOH与表面吸附的O中心自由基之间的相互作用，从而促进后续的C-C断裂。这实现了将KA油电重整为己二酸盐和纯H2的高效双电极系统。
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.