Nickel Site Modification by High-Valence Doping: Effect of Tantalum Impurities on the Alkaline Water Electro-Oxidation by NiO Probed by Operando Raman Spectroscopy.

In an effort to support the large-scale implementation of clean hydrogen in industry and society, the electrolytic decomposition of water is considered a realistically enticing prospect, provided the guarantee of affordable and durable material components. Within alkaline systems, earth-abundant electrocatalysts could provide both these requirements. However, a continued exploration of the reactivity and the causes behind different behaviors in performance are necessary to guide optimization and design. In this paper, Ta-doped NiO thin films are prepared via DC magnetron sputtering (1-2-4 at % Ta) to demonstrate the effect of surface electronic modulation by non-3d elements on the catalysis of the oxygen evolution reaction (OER). Material properties of the catalysts are analyzed via Rutherford backscattering spectrometry, X-ray diffractometry, photoelectron spectroscopy, and Raman spectroscopy. Ta impurities are shown to be directly responsible for increasing the valence state of Ni sites and enhancing reaction kinetics, resulting in performance improvements of up to 64 mV at 10 mA cm relative to pristine NiO. Particularly, we show that by applying Raman spectroscopy, Ta enhances the ability to create high-valence Ni in γ-NiOOH at a lower overpotential compared to the undoped sample. The lowered overpotentials of the OER can thus be attributed to the energetically less hindered advent of the creation of γ-NiOOH species on the pre-catalyst surface: a phenomenon otherwise unresolved through simple voltammetry.