title: Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2- clusters.
abstract: 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.
authors.affiliation: 1] Interdisciplinary Nanoscience Center and Department of Physics and Astronomy, Aarhus University, DK-8000 Aarhus C, Denmark [2] Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA.
authors.forename: Jakob
authors.initials: J
authors.lastname: Kibsgaard
authors.affiliation: Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA.
authors.forename: Thomas F
authors.initials: TF
authors.lastname: Jaramillo
authors.affiliation: Interdisciplinary Nanoscience Center and Department of Physics and Astronomy, Aarhus University, DK-8000 Aarhus C, Denmark.
authors.forename: Flemming
authors.initials: F
authors.lastname: Besenbacher
mesh_terms: D002384:Catalysis; D020134:Catalytic Domain; D006859:Hydrogen / Q000737:chemistry*; D008982:Molybdenum / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D006859:Hydrogen; D008982:Molybdenum; C020809:tetrathiomolybdate