Electrodeposition of MoSx Hydrogen Evolution Catalysts from Sulfur-Rich Precursors

Amorphous molybdenum sulfides (a-MoSx) are known to be active electrocatalysts for the hydrogen evolution reaction (HER) but the role stoichiometry of the sulfur atoms plays in the HER activity remains unclear. In this work, we deposited thin films of a-MoSx from two thiomolybdate deposition baths with different sulfur ratios (MoS42- and Mo2S122-) and showed that the sulfur stoichiometry is controlled by the precursor of choice and the electrochemical method used to deposit the thin films. Using the Mo2S122- precursor allows access to a MoS6 thin film, with a higher S:Mo ratio than any previously reported electrodeposited films. We also examine the effect of electrochemistry on the resulting S:Mo ratio in the as prepared a-MoSx thin films. Samples with S:Mo ratios ranging from 2 to 6 were electrodeposited on glassy carbon (GC) substrates by using anodic, cathodic or cyclic voltammetry deposition. a-MoSx thin films deposited on GC were tested as HER catalysts in acidic electrolytes. The overpotentials needed to drive current densities of 10 mA/cm2 ranged from 160 mV for MoS6 samples to 216 mV for MoS2 samples signifying the important role sulfur content plays in HER activity of the prepared films. Furthermore, we characterized the deactivation of the a-MoSx films and found that the sulfur content is gradually depleted over time leading to a slow deactivation of the a-MoSx thin film catalysts. We show a facile procedure that affords a-MoSx films with high sulfur content by using S-rich precursors and highlight the role of sulfur in the prepared films for HER.