Mechanistic insights into electrocatalytic methylamine synthesis from N2 and CO2 on tetranuclear vanadium clusters supported by nitrogen-doped graphene: a computational study

Electrocatalytic synthesis of methylamine (CH 3 NH 2 ) offers an alternative approach to performing artificial nitrogen cycle relevant to that of conventional ammonia and urea molecules. However, the challenge for the methylamine electrosynthesis lies in the low polarization of the N–O bond in the raw materials or intermediates, which causes low selectivity of CH 3 NH 2 and poor energy efficiency, as well as undesired byproducts. In the present paper, we identify that a direct C–N coupling reaction of inert N 2 and CO 2 molecules catalyzed by a novel tetranuclear vanadium (V) cluster anchored on nitrogen‐doped graphene (V 4 /NG) can produce stable *N=NCOO* intermediate, which prevents the presence of N–O bond and effectively governs selectivity of CH 3 NH 2 . Our theoretical studies indicate that after N 2 and CO 2 molecules adsorb onto the surface of the V 4 /NG catalyst, a strong electron transfer process occurs from the V 4 clusters to these two substrate molecules, resulting in the formation of electron-rich and highly activated N 2 and CO 2 ; this enhances the reactivity of these two species, thereby promoting the formation of C–N bonds. We further discover that the tetranuclear V cluster decreases the energy requirement for cleaving N=N bond and protecting the key C–N bond in a series of hydrogenation steps via effective tunable bonding interactions of substrate molecules and catalyst. This work propels the development of metal‐based small cluster catalysts for the conversion of inert N 2 and CO 2 molecules to CH 3 NH 2 through electrochemical processes, providing a feasible and sustainable strategy.