Drastically enhanced hydrogen evolution activity by 2D to 3D structural transition in anion-engineered molybdenum disulfide thin films for efficient Si-based water splitting photocathodes

We synthesized transferrable and transparent anion-engineered molybdenum disulfide thin-film catalysts through a simple thermolysis method by using [(NH4)(2)MoS4] solution and powder precursors with different sulphur/phosphorus weight ratios. The synthesized sulphur-doped molybdenum phosphide (S:MoP) thin film changed from a two-dimensional van der Waals structure to a three-dimensional hexagonal structure by introduction of phosphorus atoms in the MoS2 thin film. The S:MoP thin film catalyst, which is composed of cheap and earth abundant elements, could provide the lowest onset potential and the highest photocurrent density for planar p-type Si photocathodes. The density functional theory calculations indicate that the surface of S:MoP thin films absorb hydrogen better than that of MoS2 thin films. The structurally engineered thin film catalyst facilitates the easy transfer of photogenerated electrons from the p-Si light absorber to the electrolyte. Anion-engineering of the MoS2 thin film catalyst would be an efficient way to enhance the catalytic activity for photoelectrochemical water splitting.