In Situ/Operando Capturing Unusual lr~(6+) Facilitating Ultrafast Electrocatalytic Water Oxidation

摘要

Identifying real active sites and understanding the mechanism of oxygen evolution reaction (OER) are still a big challenge today for developing efficient electrochemical catalysts in renewable energy technologies. Here, using a combined in situ/operando experiments and theory, the catalytic mechanism of the ordered OER active Co and Ir ions in Sr2CoIrO6-delta is studied, which exhibits an unprecedented low overpotential 210 mV to achieve 10 mA cm(-2), ranking the highest performance among perovskite-based solid-state catalysts. Operando X-ray absorption spectroscopies as a function of applied voltage indicates that Ir4+ ion is gradually converted into extremely high-valence Ir5+/6+, while the part of Co3+ ion is transferred into Co4+ under OER process. Density functional theory calculations explicitly reveal the order Co-O-Ir network as an origin of ultrahigh OER activity. The work opens a promising path to overcome the sluggish kinetics of OER bottleneck for water splitting via proper arrangements of the multi-active sites in catalyst.