Metal-free single atom catalysts towards efficient acetonitrile reduction to ethylamine

The electrochemical acetonitrile (CH3CN) reduction reaction is a promising route to produce ethylamine (CH3CH2NH2) under ambient conditions, but lacks efficient catalysts. The metal-free catalysts were rarely re-ported in current studies with the focus of metal-based materials. Here, we demonstrated that the metalloid boron atom can act as the highly active site for the reaction via density functional theory (DFT) computations. Using experimentally accessible C2N monolayer as substrate, three boron doped catalysts, namely B/C2N, were built, which show excellent thermodynamic and dynamic stability, high selectivity and effective poison resis-tance function toward CH3CN reduction reaction. The B/C2N can effectively capture and activate CH3CN molecule via the electron donation/back-donation process. Especially, boron-embedded C2N (Bint/C2N) pos-sesses the highest catalytic performance with the lowest limiting potential of-0.11 V. Further electronic property analyses demonstrated Bint/C2N has superior electrical conductivity and smallest work function, which is beneficial to the electron transfer. This work provides a theoretical guidance for the construction of novel and high-efficiency metal-free electrocatalysts towards the CH3CN reduction reaction.

Automated summary

Through density functional theory calculations, it was found that the metalloid boron atom can act as a highly active site for the electrochemical reduction of acetonitrile. The boron doped catalysts, specifically B/C2N, demonstrated excellent stability, selectivity, and resistance to poisoning. The boron-embedded C2N (Bint/C2N) showed the highest catalytic performance with the lowest limiting potential of -0.11 V. This work provides theoretical guidance for the development of novel and efficient metal-free electrocatalysts for the reduction of acetonitrile.