The d-orbital coupling modulation of CuNi alloy for acetonitrile electrochemical reduction and in-situ hydrogenation behavior characterization

摘要

Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the poor ethylamine Faradic efficiency(FE_(ethylamine)) and catalyst stability at the high current density prohibit this method from being practically used. Herein, CuNi alloy ultrafine-nano-particles based on the d-orbital coupling modulation were synthesized through the electrodeposition and their catalytic performance towards acetonitrile reduction reaction(ACNRR) has been systematically studied. The highest FE_(ethylamine)(97%) is achieved with the current density of-114 mA cm^(-2). For practical application, the current density can reach-602.8 mA cm^(-2) with 82.8% FE_(ethylamine)maintained. With the appearance of other organics which co-exist with acetonitrile in the SOHIO process, CuNi can also hydrogenate acetonitrile in it with more than 80% FE_(ethylamine). Our in-situ spectroscopy analysis and DFT calculations towards the acetonitrile hydrogenation behavior reveal that the evenly dispersed Ni in Cu modulates the dband so as to endow CuNi with the better acetonitrile adsorption, milder binding energy with the reaction intermediates, smaller barrier for *CH_3CH_2NH_2 desorption and higher ability for H_2O dissociation to provide *H.