A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides.

This work explores the opportunity to substantially reduce the cost of hydrogen evolution reaction (HER) catalysts by supporting monolayer (ML) amounts of precious metals on transition metal carbide substrates. The metal component includes platinum (Pt), palladium (Pd), and gold (Au); the low-cost carbide substrate includes tungsten carbides (WC and W(2)C) and molybdenum carbide (Mo(2)C). As a platform for these studies, single-phase carbide thin films with well-characterized surfaces have been synthesized, allowing for a direct comparison of the intrinsic HER activity of bare and Pt-modified carbide surfaces. It is found that WC and W(2)C are both excellent cathode support materials for ML Pt, exhibiting HER activities that are comparable to bulk Pt while displaying stable HER activity during chronopotentiometric HER measurements. The findings of excellent stability and HER activity of the ML Pt-WC and Pt-W(2)C surfaces may be explained by the similar bulk electronic properties of tungsten carbides to Pt, as is supported by density functional theory calculations. These results are further extended to other metal overlayers (Pd and Au) and supports (Mo(2)C), which demonstrate that the metal ML-supported transition metal carbide surfaces exhibit HER activity that is consistent with the well-known volcano relationship between activity and hydrogen binding energy. This work highlights the potential of using carbide materials to reduce the costs of hydrogen production from water electrolysis by serving as stable, low-cost supports for ML amounts of precious metals.