Abstract

AbstractElectrochemical acetonitrile hydrogenation compared with thermocatalytic hydrogenation provides a potential route to produce ethylamine in mild conditions. It is challenging to suppress the C–C coupling for improving ethylamine selectivity. Here, Ru‐supported Cu nanowire catalysts (Ru‐Cu NWs) are designed to achieve nearly 100% specific selectivity of ethylamine without coupling byproducts. In situ vibrational spectroscopy and electron spin resonance results reveal that the Ru‐Cu NWs provide a high active adsorption hydrogen (H*) coverage at the electrified interface so that the imine intermediates are more readily hydrogenated to generate ethylamine, thus suppressing the C–C coupling. Density functional theory calculations disclose that the formation of H* occurs more readily over Ru‐Cu NWs than Cu NWs. Moreover, the presence of Ru changes the potential‐determining step and facilitates the entire hydrogenation process. The strategy and understanding established here can be extended to other electrocatalytic hydrogenation reactions.

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