Multiple Secondary Bond-Mediated C–N Coupling over N-Doped Carbon Electrocatalysts

Electrocatalytic C–N reductive coupling offers a sustainable and eco-friendly approach to producing value-added oximes. The challenge lies in the overstrong chemisorption of N-containing intermediates and carbonyl compounds on metal-based catalysts, which causes low Faradaic efficiency and yield rates, as well as undesired byproducts. Here, we propose a multiple secondary bond-mediated strategy for C–N coupling toward benzaldoxime on a nitrogen-doped graphene-like carbon catalyst (NC). Integrating theoretical and experimental analyses, we demonstrate that the graphitic-N–C sites in NC promote nitrite reduction into hydroxylamine via weak electrostatic interaction. Moreover, the hydrogen bonds and π–π stacking interactions among NC, hydroxylamine, and benzaldehyde synergistically enrich the key intermediates on the catalyst surface and inhibit the side reactions, leading to a highly selective C–N coupling process. Remarkably, the NC catalyst achieves a high Faradaic efficiency of 73 ± 1% and a yield rate of 6.8 ± 0.1 mol h^–1 m^–2 for benzaldoxime electrosynthesis at an economically viable current density of 0.1 A cm^–2, as revealed by technoeconomic analysis. Our results demonstrate an appealing route for high-performance C–N coupling with enhanced economic feasibility.