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Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

ABSTRACT: Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

SUBMITTER: Birkner N

PROVIDER: S-EPMC4035946 | biostudies-literature | 2014 Apr

REPOSITORIES: biostudies-literature

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Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

Birkner Nancy N Navrotsky Alexandra A

Proceedings of the National Academy of Sciences of the United States of America 20140414 17

Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivat ...[more]

PMID: 24733903

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Project description:Fe(III) (oxyhydr)oxides are electron acceptors for some hyperthermophilic archaea in mildly reducing geothermal environments. However, the kinds of iron oxides that can be used, growth rates, extent of iron reduction, and the morphological changes that occur to minerals are poorly understood. The hyperthermophilic iron-reducing crenarchaea Pyrodictium delaneyi and Pyrobaculum islandicum were grown separately on six different synthetic nanophase Fe(III) (oxyhydr)oxides. For both organisms, growth on ferrihydrite produced the highest growth rates and the largest amounts of Fe(II), although P. delaneyi produced four times more Fe(II) (25 mM) than P. islandicum (6 mM). Both organisms grew on lepidocrocite and akaganéite and produced 2 and 3 mM Fe(II). Modest growth occurred for both organisms on goethite, hematite, and maghemite where ≤1 mM Fe(II) was produced. The diameters of the spherical mineral end-products following P. delaneyi growth increased by 30 nm for ferrihydrite and 50-150 nm for lepidocrocite relative to heated abiotic controls. For akaganéite, spherical particle sizes were the same for P. delaneyi-reacted samples and heated abiotic controls, but the spherical particles were more numerous in the P. delaneyi samples. For P. islandicum, there was no increase in grain size for the mineral end-products following growth on ferrihydrite, lepidocrocite, or akaganéite relative to the heated abiotic controls. High-resolution transmission electron microscopy of lattice fringes and selected-area electron diffraction of the minerals produced by both organisms when grown on ferrihydrite showed that magnetite and/or possibly maghemite were the end-products while the heated abiotic controls only contained ferrihydrite. These results expand the current view of bioavailable Fe(III) (oxyhydr)oxides for reduction by hyperthermophilic archaea when presented as synthetic nanophase minerals. They show that growth and reduction rates are inversely correlated with the iron (oxyhydr)oxide crystallinity and that iron (oxyhydr)oxide mineral transformation takes different forms for these two organisms.

Dataset Information

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

Publications

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

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