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

• Published in: Journal of physical chemistry. C 2019-02, Vol.123 (7), p.4274-4281
• Main Authors: Zhu, Hao-Ran, Hu, Yan-Ling, Wei, Shi-Hao, Hua, Da-Yin
• Format: Article
• Language: English
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.8b11696

On the basis of the first-principles calculation, single transition-metal (TM) atoms of first and second transition series are anchored on the β12 phase of the boron monolayer (BM) electrocatalyst for the sustainable production of ammonia (NH3) by reducing nitrogen (N2). We have found a new type of electrocatalyst, i.e., V atom support on the β12-BM (V/β12-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 N2, and the ionization of 1π orbital of N2 can greatly elongate the N–N bond length, leading to the activity enhancement of N2. We also point out that the bonding orbital (1π) and antibonding orbital (1π*) of N2 play a crucial role in increasing the activity of N2. Further, the climbing nudged elastic band method and molecular dynamics simulation indicate that V/β12-BM has high dynamic and thermodynamic stabilities. Moreover, V/β12-BM can also effectively suppress the hydrogen evolution reaction during the whole N2 reduction reaction process. So, we propose V/β12-BM as an excellent and promising catalyst for N2 reduction to NH3 at ambient conditions.