Mesoporous WCx Films with NiO-Protected Surface: Highly Active Electrocatalysts for the Alkaline Oxygen Evolution Reaction.

Metal carbides are promising materials for electrocatalytic reactions such as water electrolysis. However, for application in catalysis for the oxygen evolution reaction (OER), protection against oxidative corrosion, a high surface area with facile electrolyte access, and control over the exposed active surface sites are highly desirable. This study concerns a new method for the synthesis of porous tungsten carbide films with template-controlled porosity that are surface-modified with thin layers of nickel oxide (NiO) to obtain active and stable OER catalysts. The method relies on the synthesis of soft-templated mesoporous tungsten oxide (mp. WOx ) films, a pseudomorphic transformation into mesoporous tungsten carbide (mp. WCx ), and a subsequent shape-conformal deposition of finely dispersed NiO species by atomic layer deposition (ALD). As theoretically predicted by density functional theory (DFT) calculations, the highly conductive carbide support promotes the conversion of Ni2+ into Ni3+ , leading to remarkably improved utilization of OER-active sites in alkaline medium. The obtained Ni mass-specific activity is about 280 times that of mesoporous NiOx (mp. NiOx ) films. The NiO-coated WCx catalyst achieves an outstanding mass-specific activity of 1989 A gNi -1 in a rotating-disc electrode (RDE) setup at 25 °C using 0.1 m KOH as the electrolyte.