Regulating the Adsorption Configuration of Intermediates to Construct C─N Bonds From CO 2 for High‐Efficiency N , N ‐Dimethylformamide Electrosynthesis

作者：Yunhui Yan, Yun Fan, Ruiqi Wang, Junhao He, Zhuoran Lu, Yulu Yang, Zhongcheng Xia, Yuping Pan, Shifan Leng, Zhonghuan Zhu, Shuangyin Wang, Yuqin Zou · 发表于：Angewandte Chemie · 年份：2026 · DOI：10.1002/ange.4379815 · 研究领域：CO2 Reduction Techniques and Catalysts、Radical Photochemical Reactions、Carbon dioxide utilization in catalysis

ABSTRACT N, N‐Dimethylformamide (DMF) is a widely used chemical reagent often described as a “universal solvent” due to its exceptional solvating capabilities. A sustainable synthesis route involves the green electrochemical coupling of CO 2 with dimethylamine (DMA). However, the rational design of highly efficient catalysts for this transformation remains constrained by a limited mechanistic understanding of the key reactive intermediates governing the process. In this study, *COO is identified as the pivotal intermediate facilitating C─N coupling, a finding substantiated by in situ Fourier transform infrared spectroscopy (FT‐IR) and online differential mass spectrometry (DEMS). Complementary Raman spectroscopy analyses further revealed that the intermediate adopts a stable chair‐like configuration, characterized by dual‐coordinated adsorption through both C and O atoms. Based on these mechanistic insights, a ZnCu catalyst was engineered that facilitates efficient CO 2 activation while simultaneously stabilizing this adsorption configuration, thereby enhancing the C─N coupling pathway. As a result, a DMF Faradaic efficiency (FE DMF ) of 51% and a production rate of 575 mmol·g −1 ·h −1 are achieved, outperforming all previously reported catalytic systems under comparable conditions. This study establishes a robust framework for understanding and optimizing C─N coupling via precise intermediate stabilization.