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 MoS 2 , amorphous MoS x , 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.

Photoelectrochemical water splitting is a promising route for the renewable production of hydrogen fuel. This work presents the results of a technical and economic feasibility analysis conducted for four hypothetical, centralized, large-scale hydrogen production plants based on this technology. The four reactor types considered were a single bed particle suspension system, a dual bed particle suspension system, a fixed panel array, and a tracking concentrator array. The current performance of semiconductor absorbers and electrocatalysts were considered to compute reasonable solar-tohydrogen conversion efficiencies for each of the four systems. The U.S. Department of Energy H2A model was employed to calculate the levelized cost of hydrogen output at the plant gate at 300 psi for a 10 tonne per day production scale. All capital expenditures and operating costs for the reactors and auxiliaries (compressors, control systems, etc.) were considered. The final cost varied from $1.60-$10.40 per kg H 2 with the particle bed systems having lower costs than the panel-based systems. However, safety concerns due to the cogeneration of O 2 and H 2 in a single bed system and long molecular transport lengths in the dual bed system lead to greater uncertainty in their operation. A sensitivity analysis revealed that improvement in the solar-to-hydrogen efficiency of the panel-based systems could substantially drive down their costs. A key finding is that the production costs are consistent with the Department of Energy's targeted threshold cost of $2.00-$4.00 per kg H 2 for dispensed hydrogen, demonstrating that photoelectrochemical water splitting could be a viable route for hydrogen production in the future if material performance targets can be met. Broader contextAs global energy consumption continues to rise, it is imperative that we develop renewable alternatives to the fossil fuel energy sources that currently power our civilization, curb CO 2 emissions, and secure a permanent energy supply for the future. Although the solutions to these global challenges are likely to consist of many different energy storage and conversion technologies, sustainably produced chemical fuels will likely play an important role due to their high energy density. Hydrogen gas is an especially promising energy carrier, but current hydrogen production processes such as steam methane reforming are unsustainable. Photoelectrochemical (PEC) water splitting is an alternative process that enables sustainable hydrogen production from water using the energy from sunlight. PEC water splitting has been demonstrated on the laboratory scale, but it has never been implemented on a large scale relevant to the global energy demand, so the prospects for scaling up this process have remained controversial. The present paper addresses the technical and economic feasibility of plants producing hydrogen via PEC water splitting. We establish practical operating efficiencies for PEC reactors, detail four potential reactor and centralized plant designs, and discuss the...

We present a scalable wet chemical synthesis for a catalytically active nanostructured amorphous molybdenum sulfide material. The catalyst film is one of the most active nonprecious metal materials for electrochemical hydrogen evolution, drawing 10 mA/cm 2 at ∼200 mV overpotential. To identify the active phase of the material, we perform X-ray photoelectron spectroscopy after testing under a variety of conditions. As deposited, the catalyst resembles amorphous MoS 3 , but domains resembling MoS 2 in composition and chemical state are created under reaction conditions and may contribute to this material's high electrochemical activity. The activity scales with electrochemically active surface area, suggesting that the rough, nanostructured catalyst morphology also contributes substantially to the film's high activity. Electrochemical stability tests indicate that the catalyst remains highly active throughout prolonged operation. The overpotential required to attain a current density of 10 mA/ cm 2 increases by only 57 mV after 10 000 reductive potential cycles. Our enhanced understanding of this highly active amorphous molybdenum sulfide hydrogen evolution catalyst may facilitate the development of economical electrochemical hydrogen production systems.

A volcano relationship exists between hydrogen evolution activities and hydrogen adsorption free energies for transition metal phosphides. We further predict and confirm that Fe0.5Co0.5P exhibits the highest activity.