Tailoring the Local Microenvironment of Carbon Nanotubes via Nitrogen Doping for Efficient Electrocatalytic Amidation of Toluene

Electrocatalytic C(sp3)–H amidation of hydrocarbons represents a promising strategy for the synthesis of high-value nitrogen-containing organic chemicals. Herein, we developed a nitrogen-doped carbon nanotube (N-CNTs) catalyst system to efficiently convert toluene into N-benzylacetamide under mild conditions. By modulating the electronic structure of the carbon framework through nitrogen doping, the optimized N–CNTs–400 catalyst achieved a high N-benzylacetamide yield rate of 3613.6 mmol m–2 h–1 and a Faradaic efficiency (FE) of 63.7%, significantly outperforming pure CNTs (FE: 40.8%) and previously reported electrocatalysts. Experimental and density functional theory (DFT) studies revealed that the incorporation of nitrogen species (pyridinic N, pyrrolic N, and graphitic N) boosted the catalyst’s electronic conductivity and strengthened charge transfer interactions with toluene, thereby facilitating C–H bond activation. Specifically, pyrrolic nitrogen played a dominant role in enhancing the bonding capability between *C6H5CH3 and *CH3CN, and promoting C–N bond formation via nucleophilic attack. This work underscores the crucial role of the doping effect in optimizing electrocatalytic hydrocarbon amidation and offers a new direction for the design of efficient and sustainable amide electrosynthesis catalysts.