Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An in Situ Soft X-ray Absorption Spectroscopy Study | Zendy

Marcel Risch | Zendy; Kelsey A. Stoerzinger | Zendy; Binghong Han | Zendy; Tom Regier | Zendy; Derek Peak | Zendy; Sayed Youssef Sayed | Zendy; Chao Wei | Zendy; Zhichuan J. Xu | Zendy; Yang ShaoHorn | Zendy

Open Access

Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An in Situ Soft X-ray Absorption Spectroscopy Study

Author(s) -

Marcel Risch,

Kelsey A. Stoerzinger,

Binghong Han,

Tom Regier,

Derek Peak,

Sayed Youssef Sayed,

Chao Wei,

Zhichuan J. Xu,

Yang ShaoHorn

Publication year - 2017

Publication title -

the journal of physical chemistry c

Language(s) - English

Resource type - Journals

eISSN - 1932-7455

pISSN - 1932-7447

DOI - 10.1021/acs.jpcc.7b05592

Subject(s) - manganese , redox , x ray absorption spectroscopy , oxygen evolution , catalysis , chemistry , valence (chemistry) , oxygen , inorganic chemistry , electrocatalyst , absorption spectroscopy , xanes , oxide , extended x ray absorption fine structure , electrochemistry , spectroscopy , electrode , biochemistry , physics , organic chemistry , quantum mechanics

Manganese oxides with rich redox chemistry have been widely used in (electro)catalysis in applications of energy and environmental consequence. While they are ubiquitous in catalyzing the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), redox processes occurring on the surface of manganese oxides are poorly understood. We report valence changes at OER- and ORR-relevant voltages of a layered manganese oxide film prepared by electrodeposition. X-ray absorption spectra were collected in situ in O2-saturated 0.1 M KOH using inverse partial fluorescence yield (IPFY) at the Mn L3,2-edges and partial fluorescence yield (PFY) at the O K-edge. Overall, we found reversible yet hysteretic Mn redox and qualitatively reproducible spectral changes by Mn L3,2 IPFY XAS. Oxidation to a mixed Mn3+/4+ valence preceded the oxygen evolution at 1.65 V vs RHE, while manganese reduced below Mn3+ and contained tetrahedral Mn2+ during oxygen reduction at 0.5 V vs RHE. Analysis of the pre-edge in O K-edge XAS pr...

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