Electrochemical coupling of carbon monoxide and amine on iodide coordination stabilized Cuδ+ site
Yun Fan, Yunhui Yan, Qizheng An, Zhongcheng Xia, Yuping Pan, Yuxuan Lu, Zhonghuan Zhu, Ruiqi Wang, Qinghua Liu, Yuqin Zou, Yongjun Li, Shuangyin Wang
Abstract
The use of renewable electricity to drive the electrocatalytic coupling of CO with nitrogen-containing organics offers a promising strategy for producing high-value chemicals. In this work, we conduct a systematic investigation of the coordination effect between iodide and copper oxide to generate Cuδ+ active sites. These Cuδ+ sites enable the electrosynthesis of dimethylacetamide from CO and dimethylamine. Through precise regulation of the electrode surface microenvironment, a dimethylacetamide Faradaic efficiency of 45.6% is achieved at a partial current density of 182.4 mA·cm-2, with a production rate of 435.9 mmol·gcat.−1·h-1 and selectivity approaching 70%. Mechanistic studies reveal that specific adsorption of I- forms an iodide-enriched Cu0/Cu+ interface that synergistically promotes dimethylacetamide formation by enhancing adsorption of ketene intermediates (*CCO) and facilitating C–N bonds formation. This anion-coordination interfacial engineering strategy demonstrates broad applicability for synthesizing various acetamide derivatives from CO2/CO and amine, providing a foundational framework for electrocatalytic C-N coupling in acetamide synthesis. The electrocatalytic C-N coupling of CO and organic nitrogen provides a promising strategy for producing high-value chemicals. Here, the authors report an iodide ion coordination effect that generates Cuδ+ active sites, enabling the efficient electrosynthesis of acetamide from CO and amine.