Abstract

In this study, a simple and versatile strategy is demonstrated to create acid-like local environments (ALLE) to boost alkaline hydrogen evolution reaction (HER) kinetics of Pt/C, Pt/CoS2, and other electrocatalysts by introducing a local electric field (LEF) stemming from the polar-faceted cubic CeO2 (C–CeO2). The surface polarity of the C–CeO2 facets is confirmed by trimethylphosphine oxide-31P nuclear magnetic resonance. Operando Raman scattering provides evidence that H3O+ intermediates produce the ALLE. This ALLE shows great enhancement in alkaline HER with activities of the C–CeO2 modified Pt/C and Pt/CoS2 promoted by 2.5 and 5.5 times compared to the counterparts, respectively. The LEF changes the mechanism from slow Volmer–Heyrovsky to fast Volmer–Tafel process. As a result, Pt/CoS2 + C–CeO2 shows a small Tafel slop of 23.8 mV dec−1 and low overpotentials of 20 and 59 mV at current densities of 10 and 100 mA cm−2, respectively. Importantly, the LEF produces similar effects in other electrocatalysts.

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