Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials

We discuss recent developments in nanostructured molybdenum sulfide catalysts for the electrochemical hydrogen evolution reaction. To develop a framework for performing consistent and meaningful comparisons between catalysts, we review standard experimental methodologies for measuring catalyst performance and define two metrics used in this perspective for comparing catalyst activity: the turnover frequency, an intrinsic activity metric, and the total electrode activity, a device-oriented activity metric. We discuss general strategies for synthesizing catalysts with improved activity, namely, increasing the number of electrically accessible active sites or increasing the turnover frequency of each site. Then we consider a number of state-of-the-art molybdenum sulfide catalysts, including crystalline MoS2, amorphous MoSx, and molecular cluster materials, to highlight these strategies in practice. Comparing these catalysts reveals that most of the molybdenum sulfide catalysts have similar active site turnover frequencies, so the total electrode activity is primarily determined by the number of accessible active sites per geometric electrode area. Emerging strategies to overcome current catalyst limitations and potential applications for molybdenum sulfide catalysts including photoelectrochemical water splitting devices and electrolyzers are also considered.