Computational Design of Single-Molybdenum Catalysts for the Nitrogen Reduction Reaction

Starting from molybdenum (Mo) embedded in black phosphorus, 17 single-Mo catalysts with various combinations of ligands, including phosphorous (P), boron (B), nitrogen (N), sulfur (5), and carbon (C), have been computationally examined as catalysts for the nitrogen reduction reaction. Among them, Mo PC2, Mo PB2, and Mo BC2 have been identified as the most promising catalysts, offering an overall overpotential less than 0.60 V. Mo-BC2 is particularly attractive as it also shows a high nitrogen reduction reaction selectivity over the hydrogen evolution reaction. Such high performance is originated essentially from the mediation of the ligands, which effectively shift the d-band center of the Mo atom toward the Fermi energy.