Benchmarking Molybdenum-Based Materials as Cathode Electrocatalysts for Proton Exchange Membrane Water Electrolysis: Can These Compete with Pt?

Progress in catalysis is driven by society's needs. The development of new electrocatalysts to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks for today's scientists and engineers. The electrochemical splitting of water into hydrogen and oxygen has been known for over 200 years, but in the last decade and motivated by the perspective of solar hydrogen production, new catalysts made of earth-abundant materials have emerged. Here we present an overview of recent developments in the non-noble metal catalysts for electrochemical hydrogen evolution reaction (HER). Emphasis is given to the nanostructuring of industrially relevant hydrotreating catalysts as potential HER electrocatalysts. The new syntheses and nanostructuring approaches might pave the way for future development of highly efficient catalysts for energy conversion.

In this review, the fundamental, current status and challenges of different types of HER electrocatalysts are highlighted. The hydrogen evolution reaction plays a decisive role in a range of electrochemical and photoelectrochemical devices. It requires efficient and robust electrocatalysts to lower the reaction overpotential and minimize energy consumption. Over the last decade, we have witnessed a rapid rise in new electrocatalysts, particularly those based on non-precious metals. Some of them approach the activity of precious metal benchmarks. Here, we present a comprehensive overview of the recent developments of heterogeneous electrocatalysts for the hydrogen evolution reaction. Detailed discussion is organized from precious metals to non-precious metal compounds including alloys, chalcogenides, carbides, nitrides, borides and phosphides, and finally to metal-free materials. Emphasis is placed on the challenges facing these electrocatalysts and solutions for further improving their performance. We conclude with a perspective on the development of future HER electrocatalysts.

Molybdenum carbide has been proposed as a possible alternative to platinum for catalyzing the hydrogen evolution reaction (HER). Previous studies were limited to only one phase, β-Mo2C with an Fe2N structure. Here, four phases of Mo-C were synthesized and investigated for their electrocatalytic activity and stability for HER in acidic solution. All four phases were synthesized from a unique amine-metal oxide composite material including γ-MoC with a WC type structure which was stabilized for the first time as a phase pure nanomaterial. X-ray photoelectron spectroscopy (XPS) and valence band studies were also used for the first time on γ-MoC. γ-MoC exhibits the second highest HER activity among all four phases of molybdenum carbide, and is exceedingly stable in acidic solution.