Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale

Kelsey A. Stoerzinger; Marcel Risch; Jin Suntivich; W. M. Lü; Jigang Zhou; Michael D. Biegalski; Hans M. Christen; Ariando; T. Venkatesan; Yang Shao-Horn

doi:10.1039/C3EE40321A

Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale†

Kelsey A. Stoerzinger,^ab Marcel Risch,^b Jin Suntivich,^c W. M. Lü,^de Jigang Zhou,^f Michael D. Biegalski,^g Hans M. Christen,^g Ariando,^eh T. Venkatesan^deh and Yang Shao-Horn*^abi

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* Corresponding authors

^a Department of Materials Science & Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, USA
E-mail: shaohorn@mit. edu

^b Electrochemical Energy Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, USA

^c Harvard University Center for the Environment, Harvard University, 29 Oxford Street, Cambridge, MA, USA

^d Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, Singapore 117583, Singapore

^e NUSNNI-NanoCore, National University of Singapore, 5A Engineering Drive 1, Singapore 117411, Singapore

^f Canadian Light Source, 44 Innovation Boulevard, Saskatoon, SK, Canada

^g Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, 1 Bethel Valley Road, Oak Ridge, TN, USA

^h Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore

ⁱ Department of Mechanical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, MA, USA

Abstract

We report that the oxygen reduction reaction (ORR) activities of (001)-oriented manganese perovskite films decrease from 10 to 1 nm by more than an order of magnitude, which can be attributed to the barrier associated with interfacial band bending that impedes electron transfer to the electrolyte, and reduction of Mn³⁺ due to charge transfer from the Nb:SrTiO₃ substrate. Furthermore, we show by substitution in La_1−x(Ca,Sr)_xMnO₃ that Mn³⁺, not Mn⁴⁺, is the active valence state for ORR.

Energy & Environmental Science

Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale†

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Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale

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