以含碳、氮小分子为原料电氧化合成酰胺类化学品

doi:10.1016/S1872-2067(25)64855-8

催化学报 ›› 2026, Vol. 80: 1-6.DOI: 10.1016/S1872-2067(25)64855-8

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以含碳、氮小分子为原料电氧化合成酰胺类化学品

马爱静^a^,^b, 沈柏安^c, 郭明昊^b^,^c, 郭成英^b^,^c, 于一夫^b^,^c^,^*()

^a天津工业大学化学工程与技术学院, 先进分离膜材料国家重点实验室, 天津绿色化学技术与过程工程重点实验室, 天津 300387
^b海河可持续化学转化实验室, 天津 300192
^c天津大学化学工程与技术学院, 分子+研究院, 天津 300072

收稿日期:2025-06-20 接受日期:2025-08-29 出版日期:2026-01-18 发布日期:2026-01-05
通讯作者: 于一夫
基金资助:
天津科技计划(24YDTPJC00050);海河可持续化学转化实验室(24HHWCSS00009)

Electro-oxidation synthesis of amides from carbon- and nitrogen-containing small molecules

Aijing Ma^a^,^b, Baian Shen^c, Minghao Guo^b^,^c, Chengying Guo^b^,^c, Yifu Yu^b^,^c^,^*()

^aState Key Laboratory of Advanced Separation Membrane Materials, Tianjin Key Laboratory of Green Chemical Technology and Process Engineering, School of Chemical Engineering and Technology, Tiangong University, Tianjin 300387, China
^bHaihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
^cInstitute of Molecular Plus, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2025-06-20 Accepted:2025-08-29 Online:2026-01-18 Published:2026-01-05
Contact: Yifu Yu
About author:Yifu Yu received his B.E. and M.E. degrees in chemical engineering from Tianjin University. He obtained his Ph.D. degree in chemical engineering from the same university in 2014. He worked as a postdoctoral fellow in Prof. Hua Zhang’s group in the School of Materials Science and Engineering, Nanyang Technological University, Singapore, from 2014 to 2017. He is currently a Professor at Institute of Molecular Plus in Tianjin University. His research interests focus on heterogeneous catalysis of nitrogen-containing small molecules.
Supported by:
Tianjin Science and Technology Program(24YDTPJC00050);Haihe Laboratory of Sustainable Chemical Transformations for financial support(24HHWCSS00009)

摘要/Abstract

摘要：

从“碳中和”角度出发, 利用电化学技术将含碳和含氮的小分子进行偶合升级转化成更高附加值的酰胺类化学品, 颇具吸引力. 目前, 电催化酰胺合成通常采用电还原过程中碳−氮键的构筑, 在此过程中不可避免的发生析氢反应, 导致酰胺的法拉第效率较低. 同时, 与共还原反应匹配的阳极反应为非必需的析氧反应, 降低了能量利用效率. 电氧化驱动廉价的含碳和含氮小分子偶合构建碳−氮键, 热力学更有利, 可以提高能量效率, 近期成为一个新兴的研究热点. 在该领域中, 抑制原料的单独氧化成为一大挑战. 基于此, 本文重点综述了电氧化合成酰胺的最新进展以及可能的反应机制, 并深入讨论了电氧化合成酰胺的应用前景和发展潜力. 此外, 针对当前研究现状本文还提出了未来发展方向.

本文从电氧化醇氨耦联反应可能的反应机理入手, 讨论了两种可能的反应路径: (1) 由甲醇氧化产生的甲醛与氨反应生成半缩醛中间体, 随后脱水生成甲酰胺. (2)甲醛与氨反应生成了亚胺中间体, 该中间体随后被氧化成腈, 然后又水解生成甲酰胺. 介绍了电氧化醇氨耦联反应的反应条件、检测方法、原位表征方法以及理论计算的研究成果, 在总结了影响催化剂催化性能因素的基础上, 提出了催化剂的设计策略以及催化体系的改进方法, 并对未来电化学合成酰胺领域的发展提出展望. 首先, 基于反应机制以及反应中间体的吸附路径等方面讨论了电氧化醇氨耦联的关键难点. 为了进一步提高碳和氮的原子利用效率, 同时在两个电极上产生酰胺的阴极-阳极耦合系统具有很大的潜力. 该系统旨在协同氧化与还原过程, 使得阴极与阳极两侧电化学反应都能生成高附加值酰胺类化学品. 这不仅是一项技术进步, 而且是从过程强化向系统集成的转变. 另外, 电氧化反应过程中甲醛是形成碳−氮键的关键中间体, 但醛基中间体极易过度氧化产生甲酸副产物, 这降低了酰胺的选择性和产率. 为解决该问题, 合理设计催化剂, 调节其电子结构保证醇类氧化活化的基础上抑制醛基中间体的过度氧化尤为重要. 催化剂合金设计、杂原子掺杂、界面工程、非晶化处理、单原子调制等可控策略有助于抑制副反应的进行. 最后, 介绍了电氧化醇氨耦联反应在电合成领域的应用前景, 提出了当前方向所面临的挑战和解决策略.

综上, 目前研究取得的进展说明电氧化制备酰胺类化学品具有广阔的研究前景, 并且该技术用于工业生产具有可行性, 这为实现碳循环、氮循环的闭环带来了新的机遇. 尽管电氧化醇氨耦联面临动力学不匹配、容易单独氧化等难题, 但随着理论与实验研究的结合, 原位表征技术不断地开发利用, 未来高效、稳定的新型电氧化醇氨耦联催化剂会不断的出现. 本文也为电氧化醇氨耦联合成酰胺类化学品的未来研究方向提供理论参考.

关键词: 酰胺类化学品, 电合成, 氧化耦联, C-N键, 可持续原料

Abstract:

Electrochemical synthesis of amides from carbon- and nitrogen-containing small molecules is alluring from the view of carbon neutrality. Previous works were mainly focused on electro-reduction coupling of C-N bond to prepare amides coupled with the useless oxygen evolution reaction on the anode. But, the competing hydrogen evolution reaction is more favorable in dynamics on the cathode, severely retarding the Faradaic efficiency of the amides. Very recently, electro-oxidation construction of C-N bond via coupling the cheap C- and N-containing small molecules to achieve high energy efficiency emerges as a rising star, while the big challenge lies in preventing the sole oxidation of feedstocks. In this perspective, we highlight the recent progress in anodic electro-oxidation synthesis of amides and the potential reaction mechanism. We also discuss the application potential and the development opportunities of the electro-oxidation strategy for amides synthesis from carbon- and nitrogen-containing small molecules.

Key words: Amides, Electrosynthesis, Oxidation coupling, C-N bond, Sustainable feedstocks

马爱静, 沈柏安, 郭明昊, 郭成英, 于一夫. 以含碳、氮小分子为原料电氧化合成酰胺类化学品[J]. 催化学报, 2026, 80: 1-6.

Aijing Ma, Baian Shen, Minghao Guo, Chengying Guo, Yifu Yu. Electro-oxidation synthesis of amides from carbon- and nitrogen-containing small molecules[J]. Chinese Journal of Catalysis, 2026, 80: 1-6.

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图/表 4

Fig. 1. Comparison of formamide production technology. The manufacture of amides from traditional thermal-catalytic (a) and sustainable electro-catalytic (b) strategies.

Fig. 2. Reaction mechanism analysis [3]. (a) The possible formamide formation pathways. (b) Isotope-labeled in situ ATR-FTIR measurements using 14NH4+ and 15NH4+ as nitrogen source.

Fig. 3. Practical application potential for electro-oxidation synthesis of amides. (a) TEA of the levelized cost of formamide electrosynthesis as a function of Faradaic efficiency and renewable energy cost [3]. (b) The image of a pilot-scale electrolyzer incorporating BDD anode [24]. (c) The scheme of scale-up electrolysis device [24].

Fig. 4. The scheme of amide electrosynthesis strategies. (a) The strategy of simultaneous anodic and cathodic amide formation. (b) The strategy of avoiding aldehyde over-oxidation.

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以含碳、氮小分子为原料电氧化合成酰胺类化学品

Electro-oxidation synthesis of amides from carbon- and nitrogen-containing small molecules

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