The transition metal doped B cluster (TM4B18) as catalysis for nitrogen fixation

Renewable electrically/light-driven nitrogen reduction from earth's abundant nitrogen is considered one of the most attractive strategies for clean energy transport and storage through nitrogen cycle. To this end, developing inexpensive, rich and excellent performance catalysts for nitrogen reduction reaction (NRR) is essential but challenging. Here, we systematically studied 18 kind of transition metal boron clusters TM4B18 (TM = 3d, 4d and 5d) as promising photocatalytic catalysis for NRR. Our first-principles calculations demonstrate that these TM4B18 clusters possess outstanding water environment stability and high selectivity for NRR under hydrogen evolution reaction (HER) side reaction. In particular, three candidate catalysts (Zr4B18, V4B18 and Mn4B18) for ammonia synthesis with excellent performance are selected by high-throughput screening of TM4B18 materials using a "Four-Step" method. Most notably, Zr4B18 cluster performs best with onset potential lower-0.50 eV through the enzymatic mechanism, such result is owing to the part of occupied d orbitals of the active metal atoms. Furthermore, these TM4B18 clusters with appropriate energy gap that is able to absorb light from the visible to ultraviolet to driven NRR. These theoretical researches offer vital physical views for using the superior transition metal doped B cluster materials for driving by solar energy and ammonia production.