Enhanced electrocatalytic CH amination of toluene via tailored interfacial microenvironment

Electrocatalytic CH amination of hydrocarbons is a promising avenue for the synthesis of high-value CN compounds. However, efficient activation of CH bonds remains a significant challenge in electrocatalytic CN coupling. Herein, we present a novel strategy to enhance the electrocatalytic conversion of toluene to N-benzylacetamide through a Ritter–type reaction by engineering a hydrophobic electrode–electrolyte interface using polytetrafluoroethylene (PTFE)-coated carbon paper (CP). The hydrophobic CP-based electrode exhibited a superior N-benzylacetamide productivity of 1860.9 mmol m⁻²h⁻¹ and a substantially higher Faradaic efficiency (FE) of 70.1 % compared to pure CP (41.5 %). Experimental results and density functional theory (DFT) calculations reveal that the PTFE coating promotes toluene adsorption and efficiently lowers the energy barrier for toluene dehydrogenation. Additionally, the hydrophobic interface effectively hinders water adsorption on the electrode, suppressing the competitive water oxidation reaction. This study underscores the crucial role of interfacial engineering in optimizing electrocatalytic CN coupling reactions for the sustainable synthesis of high-value amide compounds.