Mixed-Valent Mn16-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties.

Autor: Haider A; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Ibrahim M; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Bassil BS; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.; Department of Chemistry, Faculty of Sciences, University of Balamand , P.O. Box 100, Tripoli, Lebanon., Carey AM; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Viet AN; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Xing X; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Ayass WW; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Miñambres JF; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany., Liu R; Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences , 100190, Beijing, China., Zhang G; Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences , 100190, Beijing, China., Keita B; Université Paris-Sud, Laboratoire de Chimie-Physique, UMR 8000 CNRS , Orsay, F-91405, France., Mereacre V; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany., Powell AK; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) , Engesserstrasse 15, 76131 Karlsruhe, Germany., Balinski K; Department of Physics and Center of Physics and Chemistry of New Materials, Osnabrück University , D-49069 Osnabrück, Germany., N'Diaye AT; Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States., Küpper K; Department of Physics and Center of Physics and Chemistry of New Materials, Osnabrück University , D-49069 Osnabrück, Germany., Chen HY; TUM CREATE , 1 CREATE Way, #10-02 CREATE Tower, 138602 Singapore.; Department of Chemistry, Technische Universität München , Lichtenbergstraße 4, 85748 Garching, Germany., Stimming U; TUM CREATE , 1 CREATE Way, #10-02 CREATE Tower, 138602 Singapore.; Department of Chemistry, Technische Universität München , Lichtenbergstraße 4, 85748 Garching, Germany.; School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne, NE1 7RU, United Kingdom., Kortz U; Department of Life Sciences and Chemistry, Jacobs University , P.O. Box 750 561, 28725 Bremen, Germany.
Jazyk: angličtina
Zdroj: Inorganic chemistry [Inorg Chem] 2016 Mar 21; Vol. 55 (6), pp. 2755-64. Date of Electronic Publication: 2016 Mar 02.
DOI: 10.1021/acs.inorgchem.5b02503
Abstrakt: The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [Mn(III)10Mn(II)6O6(OH)6(PO4)4(A-α-SiW9O34)4](28-) (1) and [Mn(III)4Mn(II)12(OH)12(PO4)4(A-α-SiW9O34)4](28-) (2) have been prepared by reaction of the trilacunary Keggin precursor [A-α-SiW9O34](10-) with either Mn(OOCCH3)3·2H2O (for 1) or MnCl2·4H2O (for 2), in aqueous phosphate solution at pH 9. Polyanions 1 and 2 comprise mixed-valent, cationic {Mn(III)10Mn(II)6O6(OH)6}(24+) and {Mn(III)4Mn(II)12(OH)12}(24+) cores, respectively, encapsulated by four phosphate groups and four {SiW9} units in a tetrahedral fashion. Both polyanions were structurally and compositionally characterized by single-crystal XRD, IR, thermogravimetric analysis, and X-ray absorption spectroscopy. Furthermore, studies were performed probing the magnetic, electrochemical, oxidation catalytic, and Li-ion battery performance of 1 and 2.
Databáze: MEDLINE