Ambient One‐Pot Electrocatalytic Synthesis of Caprolactam From Cyclohexanone and Nitrate Over Ag‐Ag ₄ Sn‐SnO ₂ Nanoparticles

Caprolactam (CPL), a monomer of nylon‐6 widely used in automotive, machinery, and electronics, is traditionally synthesized from cyclohexanone (CYC) through a complex process that generates low‐value ammonium sulfate, leading to environmental pollution. In contrast, electrochemical methods offer a safer, greener one‐pot synthesis of CPL from waste NO 3 – , but currently, the coupling of CYC and NO 3 – primarily produces cyclohexanone oxime (CHO), and the direct generation of CPL is challenging. Here, we report for the first time the electrochemical conversion of CYC and NO 3 – to high‐value CPL in a one‐pot process under ambient conditions. Using Ag‐Ag 4 Sn‐SnO 2 nanoparticle catalysts, we achieved a remarkable 96% yield and 97% selectivity for CPL electrosynthesis. In situ characterizations, control experiments, and theoretical calculations suggested the importance of balanced activation of NO 3 – and CYC substrates on the Ag‐Ag 4 Sn‐SnO 2 catalysts for achieving high‐efficient CPL electrosynthesis. The method also exhibits broad versatility in synthesizing various amide compounds, including paracetamol for antipyretic. Notably, scaling up the reactor enabled a high CPL production rate of 3.41 g h −1 g cat −1 with a 90.5% isolated yield, highlighting the potential of this technique for large‐scale electrosynthesis.