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

Lookup NU author(s): Professor Ulrich Stimming



This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0).


The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [(Mn10Mn6O6)-Mn-III-O-II(OH)(6)(PO4)(4)(A-alpha-SiW9O34)(4)](28-) (1) and [(Mn4Mn12II)-Mn-III(OH)(12)(PO4)(4)(A-alpha-SiW9O34)(4)](28-) (2) have been prepared by reaction of the trilacunary Keggin precursor [A-alpha-SiW9O34](10-) with either Mn(OOCCH3)(3)center dot 2H(2)O (for 1) or MnCl2 center dot 4H2O (for 2), in aqueous phosphate solution at pH 9. Polyanions 1 and 2 comprise mixed-valent, cationic {(MnMnI6O6)-Mn-III-I-II(OH)(6)}(24+) and {(Mn10Mn6O6)-Mn-III-O-II(OH)(6)(PO4)(4) 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, therrnogravimetric 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.

Publication metadata

Author(s): Haider A, Ibrahim M, Bassil BS, Carey AM, Viet AN, Xing XL, Ayass WW, Minambres JF, Liu RJ, Zhang GJ, Keita B, Mereacre V, Powell AK, Balinski K, N'Diaye AT, Kupper K, Chen HY, Stimming U, Kortz U

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2016

Volume: 55

Issue: 6

Pages: 2755-2764

Online publication date: 02/03/2016

Acceptance date: 01/01/1900

Date deposited: 05/05/2016

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society


DOI: 10.1021/acs.inorgchem.5b02503


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Funder referenceFunder name
National Research Foundation of Singapore
Higher Education Commission of Pakistan
Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT)
Jacobs University
Newcastle University
2015VMA041Chinese Academy of Sciences President's International Fellowship Initiative
21371173National Science Foundation of China
CM1203CMST COST Action
DE-AC02-05CH11231Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy
KO 2288/20-1German Science Foundation (DFG)