High-throughput screening and research of nitrogen reduction on 2D metal–organic framework: First-principles study

Developing efficient nitrogen reduction reaction (NRR) catalysts remains challenging. Two-dimensional metal–organic frameworks (MOFs) stand out because of their large holes and high metal utilization. Based on first-principles high-throughput calculations, we studied the catalytic capacity of MOF catalyst TM3 (HITP)2 for NRR. Our calculated results indicate that among 29 catalytic structures, Mo3(HITP)2 and Os3(HITP)2 exhibit excellent activity for NRR, with the overpotential being 0.39 and 0.43 V, respectively. The unoccupied 4d orbitals of Mo are especially closer to the antibonding N-2p orbitals, leading to better nitrogen activation and lower overpotential. In addition, a descriptor related to charge variation and the electronegativity of metals and coordinating atoms is established, which has a good volcano plot relationship with the limiting potential of NRR and can provide ideas for catalyst screening. This research contributes valuable insights for the screening of NRR catalysts based on MOF.