Manganese oxides: Parallels between abiotic and biotic structures

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作者
Saratovsky, Ian [1 ,3 ]
Wightman, Peter G. [2 ,3 ]
Pastén, Pablo A. [4 ]
Gaillard, Jean-François [2 ,3 ]
Poeppelmeier, Kenneth R. [1 ,3 ]
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[1] Department of Chemistry, Northwestern University, Evanston, IL 60208, United States
[2] Department of Environmental Engineering and Science, Northwestern University, Evanston, IL 60208, United States
[3] Institute for Environmental Catalysis, Northwestern University, Evanston, IL 60618, United States
[4] Departamento de Ingeniería Hidráulica y Ambiental, Pontifica Universidad Católica de Chile, Santiago, Codigo Postal 6904411, Chile
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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&middot 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. © 2006 American Chemical Society;
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页码:11188 / 11198
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