The Role of Discrepant Reactive Intermediates on Ru-Ru2 P Heterostructure for pH-Universal Hydrogen Oxidation Reaction

Angew Chem Int Ed Engl. 2023 Jan 9;62(2):e202215585. doi: 10.1002/anie.202215585. Epub 2022 Dec 7.

Abstract

Developing highly efficient electrocatalysts for hydrogen oxidation reaction (HOR) under alkaline media is essential for the commercialization of alkaline exchange membrane fuel cell (AEMFC). However, the kinetics of HOR in alkaline media is complicated, resulting in orders of magnitude slower than that in acid, even for the state-of-the-art Pt/C. Here, we find that Ru-Ru2 P/C heterostructure shows HOR performance with a non-monotonous variation in a whole pH region. Unexpectedly, an inflection point located at pH≈7 is observed, showing an anomalous behavior that HOR activity under alkaline media surpasses acidic media. Combining experimental results and theoretical calculations, we propose the roles of discrepant reactive intermediates for pH-universal HOR, while H* and H2 O* adsorption strengths are responsible for acidic HOR, and OH* adsorption strength is essential for alkaline HOR. This work not only sheds light on fundamentally understanding the mechanism of HOR but also provides new designing principles for pH-targeted electrocatalysts.

Keywords: Apparent Hydrogen Binding Energy; Hydrogen Oxidation Reaction; Hydroxide Binding Energy; Non-Monotonous Variation; Ru-Ru2P Heterostructure.