Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters.

Identifying and understanding the active sites responsible for reaction turnover is critical to developing improved catalysts. For the hydrogen-evolution reaction (HER), MoS₂ has been identified as an active non-noble-metal-based catalyst. However, only edge sites turnover the reaction because the basal planes are catalytically inert. In an effort to develop a scalable HER catalyst with an increased number of active sites, herein we report a Mo-S catalyst (supported thiomolybdate [Mo₃S₁₃]²⁻ nanoclusters) in which most sulfur atoms in the structure exhibit a structural motif similar to that observed at MoS₂ edges. Supported sub-monolayers of [Mo₃S₁₃]²⁻ nanoclusters exhibited excellent HER activity and stability in acid. Imaging at the atomic scale with scanning tunnelling microscopy allowed for direct characterization of these supported catalysts. The [Mo₃S₁₃]²⁻ nanoclusters reported herein demonstrated excellent turnover frequencies, higher than those observed for other non-precious metal catalysts synthesized by a scalable route. [ABSTRACT FROM AUTHOR]