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

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• 作者：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
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 21, 2016
• 年：2016
• 卷：55
• 期：6
• 页码：2755-2764
• 全文大小：648K
• ISSN：1520-510X

文摘

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.