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Catalysts 2014, 4(2), 129-145; doi:10.3390/catal4020129

In Situ XANES/XPS Investigation of Doped Manganese Perovskite Catalysts

1
Institut für Materialphysik, Georg-August-Universität Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany
2
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
*
Author to whom correspondence should be addressed.
Received: 14 February 2014 / Revised: 26 March 2014 / Accepted: 1 April 2014 / Published: 23 April 2014
(This article belongs to the Special Issue Perovskite Catalysts)
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Abstract

Studying catalysts in situ is of high interest for understanding their surface structure and electronic states in operation. Herein, we present a study of epitaxial manganite perovskite thin films (Pr1−xCaxMnO3) active for the oxygen evolution reaction (OER) from electro-catalytic water splitting. X-ray absorption near-edge spectroscopy (XANES) at the Mn L- and O K-edges, as well as X-ray photoemission spectroscopy (XPS) of the O 1s and Ca 2p states have been performed in ultra-high vacuum and in water vapor under positive applied bias at room temperature. It is shown that under the oxidizing conditions of the OER a reduced Mn2+ species is generated at the catalyst surface. The Mn valence shift is accompanied by the formation of surface oxygen vacancies. Annealing of the catalysts in O2 atmosphere at 120 °C restores the virgin surfaces. View Full-Text
Keywords: catalysis; oxygen evolution; manganese perovskite; Pr1−xCaxMnO3; XANES; XPS; Mn L-edge; active state; oxygen vacancies; surface valence catalysis; oxygen evolution; manganese perovskite; Pr1−xCaxMnO3; XANES; XPS; Mn L-edge; active state; oxygen vacancies; surface valence
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Mierwaldt, D.; Mildner, S.; Arrigo, R.; Knop-Gericke, A.; Franke, E.; Blumenstein, A.; Hoffmann, J.; Jooss, C. In Situ XANES/XPS Investigation of Doped Manganese Perovskite Catalysts. Catalysts 2014, 4, 129-145.

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