Abstract

The hydrogen evolution reaction (HER) is a fundamental process in electrocatalysis and plays an important role in energy conversion for the development of hydrogen-based energy sources. However, the considerably slow rate of the HER in alkaline conditions has hindered advances in water splitting techniques for high-purity hydrogen production. Differing from well documented acidic HER, the mechanistic aspects of alkaline HER are yet to be settled. A critical appraisal of alkaline HER electrocatalysis is presented, with a special emphasis on the connection between fundamental surface electrochemistry on single-crystal models and the derived molecular design principle for real-world electrocatalysts. By presenting some typical examples across theoretical calculations, surface characterization, and electrochemical experiments, we try to address some key ongoing debates to deliver a better understanding of alkaline HER at the atomic level.

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