The production of sustainable hydrogen with water electrolyzers is envisaged as one of the most promising ways to match the continuously growing demand for renewable electricity storage. While so far regarded as fast when compared to the oxygen evolution reaction (OER), the hydrogen evolution reaction (HER) regained interest in the last few years owing to its poor kinetics in alkaline electrolytes. Indeed, this slow kinetics not only may hinder the foreseen development of the anionic exchange membrane water electrolyzer (AEMWE), but also raises fundamental questions regarding the parameters governing the reaction. In this perspective, we first briefly review the fundamentals of the HER, emphasizing how studies performed on model electrodes allowed for achieving a good understanding of its mechanism under acidic conditions. Then, we discuss how the use of physical descriptors capturing the sole properties of the catalyst is not sufficient to describe the HER kinetics under alkaline conditions, thus forcing the catalysis community to adopt a more complex picture taking into account the electrolyte structure at the electrochemical interface. This work also outlines new techniques, such as spectroscopies, molecular simulations, or chemical approaches that could be employed to tackle these new fundamental challenges, and potentially guide the future design of practical and cheap catalysts while also being useful to a wider community dealing with electrochemical energy storage devices using aqueous electrolytes.
This journal is © The Royal Society of Chemistry 2019.