电催化有机合成反应的活性和选择性调控研究进展

doi:10.16085/j.issn.1000-6613.2023-0510

摘要/Abstract

摘要：

与传统有机合成技术相比，电合成技术具有原子利用率高、反应条件温和、易控制、污染小等优势，近年来成为有机合成领域的研究热点。电化学反应主要发生在电极-溶液界面，反应物在界面处的传质、吸附和表面反应行为决定了电化学反应的活性和选择性。本文从不同的尺度综述了近年来国内外关于提升有机电合成活性和选择性的最新研究进展，重点讨论了催化剂电子结构调控、电极-溶液界面设计以及反应与传递耦合等策略对有机电合成活性和产物选择性提升的影响，提出了有机电化学反应机理、催化剂构效关系、电合成反应器、反应与分离耦合等重点研究方向，为推进有机电合成发展提供思路。

关键词: 有机电合成, 选择性, 活性, 催化剂, 多尺度

Abstract:

Compared with traditional organic synthesis techniques, electrosynthesis has many advantages such as high atom utilization, mild reaction conditions, easy reaction control, and friendly to the environment, and has become a popular research area of organic synthesis in recent years. The electrochemical reaction mainly occurs at the electrode-solution interface, and the mass transfer, adsorption and surface reaction behavior of the reactants at the interface determine the activity and selectivity of the electrochemical reaction. This paper reviewed the latest research progress on improving the activity and selectivity of organic electrosynthesis at different scales, focusing on the strategies of catalyst electronic structure regulation, electrode-solution interface design, reaction and transport coupling. It also proposed the important research directions in the future, including electrochemical organic reaction mechanism, catalyst structure-performance relation, electrosynthesis reactor, and coupling of reaction and separation, which could provide reference for the development of electrocatalytic organic synthesis.

Key words: organic electrosynthesis, selectivity, activity, catalyst, multiscale

中图分类号:

TQ151

向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.

XIANG Yang, HUANG Xun, WEI Zidong. Recent progresses in the activity and selectivity improvement of electrocatalytic organic synthesis[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4005-4014.

图/表 6

图1 RuO2-SnO2-TiO2/Ti电极用于肉桂醛（CAL）选择性加氢制备肉桂醇（COL）

图2 在1.40V vs RHE和pH=13.5下，不同催化剂的自由能变图[NiOOH (左) 和Mn-NiOOH (右) 的析氧反应 (a, b) 和胺氧化反应 (c, d) 的自由能变[22]]

图3 相应的吸附能、反应路径及反应机理图

图4 MnO2/(Ru0.3Ti0.7)O2/Ti电极歧化苯乙烯成对π电子示意图[30]

图5 环己酮在SDS修饰的层状Ni(OH)2上扩散行为的粗粒度分子动力学模拟

图6 电化学反应与传递耦合设计示例

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