Hydrogen evolution enhancement of ultra-low loading, size-selected molybdenum sulfide nanoclusters by sulfur enrichment

Size-selected molybdenum sulfide (MoS_x) nanoclusters obtained by magnetron sputtering and gas condensation on glassy carbon substrates are typically sulfur-deficient (x = 1.6 ± 0.1), which limits their crystallinity and electrocatalytic properties. Here we demonstrate that a sulfur-enriching method, comprising sulfur evaporation and cluster annealing under vacuum conditions, significantly enhances their activity towards the hydrogen evolution reaction (HER). The S-richness (x = 4.9 ± 0.1) and extended crystalline order obtained in the sulfur-treated MoS_x nanoclusters lead to consistent 200 mV shifts to lower HER onset potentials, along with two-fold and more-than 30-fold increases in turnover frequency and exchange current density values respectively. The high mass activities (∼111 mA mg⁻¹ @ 400 mV) obtained at ultra-low loadings (∼100 ng cm^-2, 5% surface coverage) are comparable to the best reported MoS₂ catalysts in the literature.