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Journal article

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

From

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.1

Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA.2

Interdisciplinary Nanoscience Center and Department of Physics and Astronomy, Aarhus University, DK-8000 Aarhus C, Denmark.3

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.

Language: English
Publisher: Nature Publishing Group UK
Year: 2014
Pages: 248-253
ISSN: 17554349 and 17554330
Types: Journal article
DOI: 10.1038/nchem.1853

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