Insights into the pH effect on hydrogen electrocatalysis.

Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future.