Hydrogen generation through electrocatalytic splitting of water, i.e., hydrogen evolution reaction (HER), is an attractive method of converting the electricity generated from renewable sources into chemical energy stored in hydrogen molecules. A wide variety of materials have been studied in an effort to develop efficient and cost-effective electrocatalysts that can replace the traditional platinum/carbon catalyst. One family of functional materials that holds promise for this application is perovskite oxides. This mini-review discusses some of the progress made in the development of HER electrocatalysts based on perovskite oxides in the past decade. Given the diverse range of possible compositions of perovskite oxides, various studies have focused on compositional modifications to develop single-phase catalysts, whereas others have investigated heterostructures and composites that take advantage of synergistic interactions of different compounds with perovskite oxides. The recent advances indicate that this family of materials have great potential for utilization in HER electrocatalysis.

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Multifunctional materials that are capable of facilitating multiple electrocatalytic processes are highly desirable. This work reports the observation of bifunctional electrocatalytic properties for water‐splitting in layered oxides, featuring 2‐dimensional layers of octahedrally coordinated transition metals separated by alkaline‐earth or rare‐earth metals. Remarkably, these materials are able to catalyze both half‐reactions of water‐splitting, i. e., oxygen‐evolution reaction (OER) and hydrogen‐evolution reaction (HER). Electrical charge‐transport studies of SrLaFe1‐xCoxO4‐δ in a wide range of temperatures, 25 to 800 °C, indicate semiconducting behavior for all three compounds, where there is a systematic increase in electrical conductivity as a function of temperature. The end member of the series, SrLaCoO4‐δ, exhibits the highest electrical charge transport and best electrocatalytic activity toward both OER and HER. This catalyst also features the highest degree of polyhedral distortion as well as the presence of oxygen‐vacancies. In addition, the transition metals in this material have a favorable electronic configuration for enhanced electrocatalytic activity.

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Development of enhanced electrocatalysts for water splitting can be a significant step toward green hydrogen generation. In this work, a remarkable enhancement of electrocatalytic properties is achieved through incorporation of...