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

Ali Haider; Masooma Ibrahim; Bassem S. Bassil; Akina M. Carey; Anh Nguyen Viet; Xiaolin Xing; Wassim W. Ayass; Juan F. Miñambres; Rongji Liu; Guangjin Zhang; Bineta Keita; Valeriu Mereacre; Annie K. Powell; Kamil Balinski; Alpha T. N'Diaye; Karsten Küpper; Han Yi Chen; Ulrich Stimming; Ulrich Kortz

doi:10.1021/acs.inorgchem.5b02503

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

Ali Haider, Masooma Ibrahim, Bassem S. Bassil, Akina M. Carey, Anh Nguyen Viet, Xiaolin Xing, Wassim W. Ayass, Juan F. Miñambres, Rongji Liu, Guangjin Zhang, Bineta Keita, Valeriu Mereacre, Annie K. Powell, Kamil Balinski, Alpha T. N'Diaye, Karsten Küpper, Han Yi Chen, Ulrich Stimming, Ulrich Kortz

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Abstract

The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [Mn^III₁₀Mn^II₆O₆(OH)₆(PO₄)₄(A-α-SiW₉O₃₄)₄]^28- (1) and [Mn^III₄Mn^II₁₂(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^III₁₀Mn^II₆O₆(OH)₆}²⁴⁺ and {Mn^III₄Mn^II₁₂(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.

Originalsprache	Englisch
Seiten (von - bis)	2755-2764
Seitenumfang	10
Fachzeitschrift	Inorganic Chemistry
Jahrgang	55
Ausgabenummer	6
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02503
Publikationsstatus	Veröffentlicht - 21 März 2016

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Haider, A., Ibrahim, M., Bassil, B. S., Carey, A. M., Viet, A. N., Xing, X., Ayass, W. W., Miñambres, J. F., Liu, R., Zhang, G., Keita, B., Mereacre, V., Powell, A. K., Balinski, K., N'Diaye, A. T., Küpper, K., Chen, H. Y., Stimming, U., & Kortz, U. (2016). Mixed-Valent Mn₁₆-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties. Inorganic Chemistry, 55(6), 2755-2764. https://doi.org/10.1021/acs.inorgchem.5b02503

@article{ecadd09a186645cfb61a9be95d6a1508,

title = "Mixed-Valent Mn16-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties",

abstract = "The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [MnIII10MnII6O6(OH)6(PO4)4(A-α-SiW9O34)4]28- (1) and [MnIII4MnII12(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 {MnIII10MnII6O6(OH)6}24+ and {MnIII4MnII12(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.",

author = "Ali Haider and Masooma Ibrahim and Bassil, {Bassem S.} and Carey, {Akina M.} and Viet, {Anh Nguyen} and Xiaolin Xing and Ayass, {Wassim W.} and Mi{\~n}ambres, {Juan F.} and Rongji Liu and Guangjin Zhang and Bineta Keita and Valeriu Mereacre and Powell, {Annie K.} and Kamil Balinski and N'Diaye, {Alpha T.} and Karsten K{\"u}pper and Chen, {Han Yi} and Ulrich Stimming and Ulrich Kortz",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = mar,

day = "21",

doi = "10.1021/acs.inorgchem.5b02503",

language = "English",

volume = "55",

pages = "2755--2764",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "6",

}

Haider, A, Ibrahim, M, Bassil, BS, Carey, AM, Viet, AN, Xing, X, Ayass, WW, Miñambres, JF, Liu, R, Zhang, G, Keita, B, Mereacre, V, Powell, AK, Balinski, K, N'Diaye, AT, Küpper, K, Chen, HY, Stimming, U & Kortz, U 2016, 'Mixed-Valent Mn₁₆-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties', Inorganic Chemistry, Jg. 55, Nr. 6, S. 2755-2764. https://doi.org/10.1021/acs.inorgchem.5b02503

TY - JOUR

T1 - Mixed-Valent Mn16-Containing Heteropolyanions

T2 - Tuning of Oxidation State and Associated Physicochemical Properties

AU - Haider, Ali

AU - Ibrahim, Masooma

AU - Bassil, Bassem S.

AU - Carey, Akina M.

AU - Viet, Anh Nguyen

AU - Xing, Xiaolin

AU - Ayass, Wassim W.

AU - Miñambres, Juan F.

AU - Liu, Rongji

AU - Zhang, Guangjin

AU - Keita, Bineta

AU - Mereacre, Valeriu

AU - Powell, Annie K.

AU - Balinski, Kamil

AU - N'Diaye, Alpha T.

AU - Küpper, Karsten

AU - Chen, Han Yi

AU - Stimming, Ulrich

AU - Kortz, Ulrich

PY - 2016/3/21

Y1 - 2016/3/21

N2 - The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [MnIII10MnII6O6(OH)6(PO4)4(A-α-SiW9O34)4]28- (1) and [MnIII4MnII12(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 {MnIII10MnII6O6(OH)6}24+ and {MnIII4MnII12(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.

AB - The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [MnIII10MnII6O6(OH)6(PO4)4(A-α-SiW9O34)4]28- (1) and [MnIII4MnII12(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 {MnIII10MnII6O6(OH)6}24+ and {MnIII4MnII12(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.

UR - http://www.scopus.com/inward/record.url?scp=84961574831&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.5b02503

DO - 10.1021/acs.inorgchem.5b02503

M3 - Article

AN - SCOPUS:84961574831

SN - 0020-1669

VL - 55

SP - 2755

EP - 2764

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 6