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

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.