Co-Embedding homonuclear Dual-Metal sites and phosphorus atom to achieve efficient methylamine electrosynthesis from carbon dioxide and nitrate

Electrocatalytic methylamine (CH 3 NH 2 , MMA) synthesis through co-reduction of carbon dioxide and nitrate emerges as a promising approach to simultaneously alleviate environmental crisis and generate valuable chemicals, yet suffering poor activity/selectivity owing to the inefficient C-N coupling process. Here, an experimentally achievable homonuclear dual-metal and phosphorus co-embedded in graphene is reported to steer C-N coupling, in which homonuclear dual-metals and phosphorus functions as active sites for nitrate and CO 2 activation, separately. The screened data show that di-copper sites perform selective reduction of NO 3 – to *NH 2 and accomplish the corresponding exothermic C-N coupling process with the low kinetic energy barrier of 0.37 eV, and the limiting potential for the CH 3 NH 2 generation is only −0.98 V. Meanwhile, Cu 2 P-N-C is an exceptional catalyst to significantly restrain the competitive and NH 3 and H 2 side production under its limiting potential. More importantly, this work provides the significance of phosphorus as the second catalytic sites on the coexistence of dispersed metal and a novel insight into the rational design of high-performance catalyst for MMA electrosynthesis.