Electrochemical C–N coupling of CO2 and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds

Abstract

Electrochemical C–N coupling reactions based on abundant small molecules (such as CO₂ and N₂) have attracted increasing attention as a new “green synthetic strategy” for the synthesis of organonitrogen compounds, which have been widely used in organic synthesis, materials chemistry, and biochemistry. The traditional technology employed for the synthesis of organonitrogen compounds containing C–N bonds often requires the addition of metal reagents or oxidants under harsh conditions with high energy consumption and environmental concerns. By contrast, electrosynthesis avoids the use of other reducing agents or oxidants by utilizing “electrons”, which are the cleanest “reagent” and can reduce the generation of by-products, consistent with the atomic economy and green chemistry. In this study, we present a comprehensive review on the electrosynthesis of high value-added organonitrogens from the abundant CO₂ and nitrogenous small molecules (N₂, NO, NO₂⁻, NO₃⁻, NH₃, etc.) via the C–N coupling reaction. The associated fundamental concepts, theoretical models, emerging electrocatalysts, and value-added target products, together with the current challenges and future opportunities are discussed. This critical review will greatly increase the understanding of electrochemical C–N coupling reactions, and thus attract research interest in the fixation of carbon and nitrogen.