Single-Metal Atom Anchored on Boron Monolayer (β12) as an Electrocatalyst for Nitrogen Reduction into Ammonia at Ambient Conditions: A First-Principles Study

On the basis of the first-principles calculation, single transition-metal (TM) atoms of first and second transition series are anchored on the phase of the boron monolayer (BM) electrocatalyst for the sustainable production of ammonia (NH3) by reducing nitrogen (N-2). We have found a new type of electrocatalyst, i.e., V atom support on the beta(12)-BM (V/beta(12)-BM), which has a low onset potential (0.28 V), low cost, high stability, high selectivity, and high efficiency under mild conditions. The difference charge density and local density of state further demonstrated that there is an "acceptance-donation" interaction between TM atom and N-2, and the ionization of In orbital of N-2 can greatly elongate the N-N bond length, leading to the activity enhancement of N-2. We also point out that the bonding orbital (1 pi) and antibonding orbital (1 pi*) of N-2 play a crucial role in increasing the activity of N-2. Further, the climbing nudged elastic band method and molecular dynamics simulation indicate that V/beta(12)-BM has high dynamic and thermodynamic stabilities. Moreover, V/beta(12)-BM can also effectively suppress the hydrogen evolution reaction during the whole N-2 reduction reaction process. So, we propose V/beta(12)-BM as an excellent and promising catalyst for N-2 reduction to NH3 at ambient conditions.