Catalyst-Support Synergy for CO₂-Involved Electrochemical C-N Coupling Reactions

Electrocatalytic coupling of CO₂ with nitrogen-containing small molecules (N₂, NO₃ ^-, NO₂ ^-, etc.) to synthesize high-value chemicals represents a promising pathway for carbon valorization, but still suffers from low C-N coupling selectivity and severe competitive side reactions arising from complex reaction pathways and multiple intermediates. Recent studies have demonstrated that the synergistic effects between catalysts and supports could effectively regulate the adsorption and transfer of key intermediates in electrosynthesis, potentially promoting the C-N coupling efficiency. Nevertheless, the rational design of support materials for constructing highly efficient supported catalysts remains a significant challenge. Here, we review the synergistic mechanisms between catalysts and supports in electrocatalytic C-N coupling reactions. The C-N coupling pathways through diverse nitrogen-containing intermediates are summarized at first. Then, the discussion focuses on three key synergistic enhancement mechanisms enabled by supporting materials, including modulating the intrinsic activity of catalysts via strong metal-support interaction, optimizing local reaction microenvironments, and facilitating the targeted transport of key intermediates. Subsequently, the design strategies and functional properties of emerging functionalized supports in boosting C-N coupling efficiency are assessed. Finally, the challenges and perspectives for future applications of electrocatalytic C-N coupling technology are outlined.