Manganese oxides

Parallels between abiotic and biotic structures

Ian Saratovsky, Peter G. Wightman, Pablo A. Pastén, Jean François Gaillard, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

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Abstract

A large number of microorganisms are responsible for the oxidation of Mn2+ (aq) to insoluble Mn3+/4+ oxides (MnO x) in natural aquatic systems. This paper reports the structure of the biogenic MnOx, including a quantitative analysis of cation vacancies, formed by the freshwater bacterium Leptothrix discophora SP6 (SP6-MnOx). The structure and the morphology of SP6-MnOx were characterized by transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), including full multiple-scattering analysis, and powder X-ray diffraction (XRD). The biogenic precipitate consists of nanoparticles that are approximately 10 nm by 100 nm in dimension with a fibrillar morphology that resembles twisted sheets. The results demonstrate that this biogenic MnO x is composed of sheets of edge-sharing of Mn4+O 6 octahedra that form layers. The detailed analysis of the EXAFS spectra indicate that 12 ± 4% of the Mn4+ layer cation sites in SPG-MnOx are vacant, whereas the analysis of the XANES suggests that the average oxidation state of Mn is 3.8 ± 0.3. Therefore, the average chemical formula of SP6-MnOx is Mn+ yMn3+ 0.12[□0.12Mn 4+ 0.88]O2· zH2O, where M n+ y represents hydrated interlayer cations, □0.12 represents Mn4+ cation vacancies within the layer, and Mn3+ 0.12 represents hydrated cations that occupy sites above/below these cation vacancies.

Original languageEnglish
Pages (from-to)11188-11198
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number34
DOIs
Publication statusPublished - Aug 30 2006

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Manganese oxide
Cations
Positive ions
Vacancies
Oxides
Leptothrix
X-Ray Absorption Spectroscopy
Oxidation
X ray absorption spectroscopy
Multiple scattering
Fresh Water
Transmission Electron Microscopy
X-Ray Diffraction
Microorganisms
Powders
Nanoparticles
X ray powder diffraction
manganese oxide
Precipitates
Spectrum Analysis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Manganese oxides : Parallels between abiotic and biotic structures. / Saratovsky, Ian; Wightman, Peter G.; Pastén, Pablo A.; Gaillard, Jean François; Poeppelmeier, Kenneth R.

In: Journal of the American Chemical Society, Vol. 128, No. 34, 30.08.2006, p. 11188-11198.

Research output: Contribution to journalArticle

Saratovsky, Ian ; Wightman, Peter G. ; Pastén, Pablo A. ; Gaillard, Jean François ; Poeppelmeier, Kenneth R. / Manganese oxides : Parallels between abiotic and biotic structures. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 34. pp. 11188-11198.
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