Building an Appropriate Active-site Motif into a Hydrogen-evolution Catalyst with Thiomolybdate [Mo3S13]2- Clusters

Overview

Journal Nat Chem

Specialty Chemistry

Date 2014 Feb 22

PMID 24557141

Citations 89

Authors

Jakob Kibsgaard

Thomas F Jaramillo

Flemming Besenbacher

Affiliations

Soon will be listed here.

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.

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