N,N-Dimethylformamide (DMF) is a versatile chemical and universal solvent that is commonly synthesized from carbon monoxide and dimethylamine (DMA) under high temperature and pressure. However, this process leads to a large amount of carbon emissions. Herein, we propose an electrochemical strategy to directly convert carbon dioxide (CO₂) and DMA to DMF under ambient conditions. Loading palladium (Pd) onto copper (Cu) nanosheet catalysts with Cu vacancies (Pd/Cu-V_Cu) enabled the efficient synthesis of DMF, and the maximum yield and faradaic efficiency reached 385 mmol·h⁻¹·g_cat. ⁻¹ and 37.5%, respectively. In situ spectroscopy and density functional theory calculations indicated that Cu vacancies (Cu-V_Cu) promoted the adsorption of CO₂ on the catalyst surface, followed by its spontaneous coupling with DMA to form the C–N bond. Pd nanoparticles accelerated the electrochemical reduction of the intermediate ∗OCN(CH₃)₂OH to ∗OCHN(CH₃)₂OH, leading to highly efficient DMF electrosynthesis. This work paves the way for the synthesis of sustainable high-value organic nitrogen compounds from CO₂.

N,N-二甲基甲酰胺 (DMF) 是一种多功能化学品和通用溶剂，通常由一氧化碳和二甲胺 (DMA) 在高温高压下合成。然而，这个过程会导致大量的碳排放。在此，我们提出了一种在环境条件下直接将二氧化碳（CO ₂ ）和DMA转化为DMF的电化学策略。将钯(Pd)负载到具有Cu空位的铜(Cu)纳米片催化剂(Pd/Cu-V _Cu )上可以实现DMF的高效合成，最大收率和法拉第效率达到385 mmol·h ^-1 ·g _cat。分别为^-1%和37.5%。原位光谱和密度泛函理论计算表明，Cu空位（Cu-V _{Cu ）促进了CO 2}在催化剂表面的吸附，随后与DMA自发偶联形成C-N键。 Pd纳米粒子加速了中间体*OCN(CH ₃ ) ₂ OH到*OCHN(CH ₃ ) ₂ OH的电化学还原，从而实现高效的DMF电合成。这项工作为从CO ₂合成可持续的高价值有机氮化合物铺平了道路。