Ab initio Screening of a Sulfur Desorbed MoS$_2$ Photocatalyst for Nitrogen Fixation

The following study investigates the thermodynamic reaction barriers during nitrogen fixation for an inorganic sulfur desorbed photocatalyst Molybdenum disulfide surface. The design space is investigated using an density functional theory (DFT) method within a space bound by MMoS$_2$ M=Mo,Fe,Co. The discussion focuses on Heyrovsky type reactions along both the associative and dissociative pathway. A key insight into the roles of the inorganic and the balance between nitrogen and hydrogen affinity, providing evidence for an optimal material that minimizes the required over-potential. It is found that phases with a higher concentration of Mo face high reaction barrier involving nitrogen, where phases with higher concentrations of Fe and Co face high reaction barriers involving hydrogen species. In the absence of kinetic considerations, the best phase was predicted to be the 1T phase with a Mo$_{0.75}$Fe$_{0.25}$S$_{2}$ composition. This phase proved to have a balance of hydrogen and nitrogen affinity and follows the dissociative pathway, which can be evolved through non-thermal methods.