LAUSR

The reaction pathway of the oxygen reduction reaction (ORR) is strongly affected by the electrolytic environment. Meanwhile, the ORR mechanism on transition-metal oxide catalysts has not been studied intensely in very concentrated alkaline solutions that are used in practical metal-air batteries. Herein, we report the in situ activation of ORR catalysis on manganese perovskite in a concentrated alkaline solution, mediated by the spontaneous formation of oxygen vacancy sites. Electrochemical analyses of the (100) epitaxial film electrodes reveal that the exchange current and electron number of the ORR on La0.7Sr0.3Mn0.9Ni0.1O3 significantly increase with the duration of the ORR when the KOH concentration is greater than 4 M. However, these values remain unchanged with time at less than 1 M KOH concentration. Operando synchrotron X-ray spectroscopy of the (100) epitaxial film confirmed that La0.7Sr0.3Mn0.9Ni0.1O3 involves the oxygen vacancy sites with the reduction of Mn atoms in concentrated KOH solution via the hydroxylation decomposition of perhydroxyl intermediates. Hence, the O2 adsorption switched from an end-on to a bidentate mode because the cooperative active sites of the oxygen vacancy and neighboring Mn allow bidentate adsorption of the dissolved O2. Due to the simultaneous interaction with the oxygen vacancy and Mn sites, the O-O bonds are activated and the potential barrier for the electron transfer to adsorbed O2 is lowered, resulting in a shift in the reaction mechanism from that involving an indirect "2 + 2" transfer pathway to a direct 4-electron pathway.