Abstract

The industrial development of acidic water splitting significantly counts on the activity associated with stability of oxygen evolution reaction (OER) electrocatalyst. In this work, we have constructed cubic Rh@Ir core–shell for acidic water splitting. The formed Rh@Ir electrocatalyst shows a high HER performance with only 29 mV overpotential for 10 mA cm−2, stemming from the upshifted and downshifted d band center of Ir and Rh, leading to a moderate hydrogen binding strength. The Ir atom donates its electrons to nearby Rh atoms triggering a high susceptibility in nucleophilic attack by H2O to generate *OOH; thereby, the overpotential required to achieve 10 mA cm−2 is 216 mV for Rh@Ir core–shell, better than commercial IrO2. Moreover, the stability is superior to commercial IrO2 and pure Ir electrocatalyst due to the strong electronic interplay in Rh@Ir contributing to a better resistance towards electrochemical dissolution proved by operando Raman and electrochemical impedance spectroscopies. Only 1.55 V is needed for Rh@Ir to drive overall water splitting at 10 mA cm−2.

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