Anisotropic Rh/Cu Nanoplates Enable Efficient Hydrogen Spillover for Acetonitrile Hydrogenation Electrocatalysis

ABSTRACT The electrocatalytic hydrogenation of acetonitrile (CH 3 CN) to industrially value‐added ethylamine (CH 3 CH 2 NH 2 ) represents a sustainable alternative to conventional thermocatalytic processes, but its efficiency is heavily limited by sluggish water dissociation kinetics and inefficient hydrogen utilization efficiency. Herein, we orchestrate a well‐designed anisotropic heterojunction electrocatalyst that structurally featured Rh nanoparticle‐dispersed on Cu nanoplates (defined as Rh/Cu PLs) for efficient CH 3 CH 2 NH 2 electrosynthesis under ambient conditions. In comparison to counterpart electrocatalysts, anisotropic Rh/Cu PLs delivered impressive electrocatalytic performance, including superior CH 3 CH 2 NH 2 Faradaic efficiency of 66.1% and yield rate of 18.6 m m g −1 h −1 as well as high cycling stability. Electrocatalytic mechanism investigations revealed that Rh sites kinetically accelerated the Volmer step of water splitting to form active hydrogen species, which were spontaneously spillovered to and stabilized on Cu sites without further coupling into molecular H 2 . Meanwhile, heterostructure lowered the energy barriers of subsequent hydrogenation pathways and thus promoted efficient electrosynthesis of CH 3 CH 2 NH 2 from CH 3 CN. This work thus poses an alternative route to design functional HJ structures for the formation and stabilization of active hydrogen radicals for efficient electrosynthesis of various important amines.