In Situ Activation of a Manganese Perovskite Oxygen Reduction Catalyst in Concentrated Alkaline Media

Yoshitaka Aoki; Kentaro Takase; Hisao Kiuchi; Damian Kowalski; Yuki Sato; Hajime Toriumi; Sho Kitano; Hiroki Habazaki

doi:10.1021/jacs.1c00449

In Situ Activation of a Manganese Perovskite Oxygen Reduction Catalyst in Concentrated Alkaline Media

J Am Chem Soc. 2021 May 5;143(17):6505-6515. doi: 10.1021/jacs.1c00449. Epub 2021 Apr 23.

Authors

Yoshitaka Aoki¹, Kentaro Takase², Hisao Kiuchi³, Damian Kowalski¹, Yuki Sato², Hajime Toriumi², Sho Kitano¹, Hiroki Habazaki¹

Affiliations

¹ Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, Hokkaido 060-8628, Japan.
² Graduate School of Chemical Sciences and Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, Hokkaido 060-8628, Japan.
³ Office of Society-Academia Collaboration for Innovation, Kyoto University, Uji, Kyoto 611-0011, Japan.

PMID: 33887903
DOI: 10.1021/jacs.1c00449

Abstract

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 La_0.7Sr_0.3Mn_0.9Ni_0.1O₃ 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 La_0.7Sr_0.3Mn_0.9Ni_0.1O₃ 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.