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  Redox Properties of Manganese-Containing Zirconia Solid Solution Catalysts Analyzed by In Situ UV–Vis Spectroscopy and Crystal Field Theory

Klokishner, S., Reu, O., Chan-Thaw, C. E., Jentoft, F. C., & Schlögl, R. (2011). Redox Properties of Manganese-Containing Zirconia Solid Solution Catalysts Analyzed by In Situ UV–Vis Spectroscopy and Crystal Field Theory. The Journal of Physical Chemistry A, 115(28), 8100-8112. doi:10.1021/jp2034054.

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 Creators:
Klokishner, Sophia1, 2, Author              
Reu, Oleg1, Author              
Chan-Thaw, Carine E.1, Author              
Jentoft, Friederike C.1, 3, Author              
Schlögl, Robert1, Author              
Affiliations:
1Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, ou_24023              
2Institute of Applied Physics of the Academy of Sciences of Moldova, ou_persistent22              
3Chemical, Biological, and Materials Engineering, University of Oklahoma School, ou_persistent22              

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Free keywords: manganese; zirconia; UV–vis spectroscopy; solid solution; crystal field theory
 Abstract: The optical absorption spectra of manganesepromoted sulfated zirconia, a highly active alkane isomerization catalyst, were found to be characterized by oxygen-to-manganese charge-transfer transitions at 300-320 nm and d-d transitions of manganese ions at 580 and 680 nm. The latter were attributed toMn4þ and Mn3þ ions, which are known to be incorporated in the zirconia lattice. The oxygen surroundings of these ions were modeled assuming a substitutional solid solution. The crystal field splittings, vibronic coupling constants, and oscillator strengths of the manganese ions were calculated on the basis of a cluster model that considers the manganese center as a complex with the adjacent ions of the lattice as ligands. The ratio of Mn3þ to Mn4þ ions was determined using the spectra and the model, and the relative concentrations of Mn2þ, Mn3þ, and Mn4þ ions were determined with the help of the average valence known from X-ray absorption data in the literature. The redox behavior of manganese-promoted sulfated zirconia in oxidizing and inert atmosphere was elucidated at temperatures ranging from 323 to 773 K.

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Language(s): eng - English
 Dates: 2011-05-272011-07-21
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jp2034054
 Degree: -

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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: 13 Volume / Issue: 115 (28) Sequence Number: - Start / End Page: 8100 - 8112 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4