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Synthesis, Crystal Structure, Electrochemistry and Electro-Catalytic Properties of the Manganese-Containing Polyoxotungstate, [(Mn(H2O)3)2(H2W12O42)]6−

1
Equipe d’Electrochimie et de Photo-électrochimie, Laboratoire de Chimie Physique, Univ Paris Sud, UMR 8000 CNRS, Université Paris-Saclay, F-91405 Orsay, France
2
Institut Lavoisier de Versailles, Université de Versailles St. Quentin, UMR 8180 CNRS, Université Paris-Saclay, F-78035 Versailles, France
3
Oregon State University, Department of Nuclear Engineering and Radiation Health Physics, Corvallis, OR 97331, USA
4
Laboratoire de Chimie Physique et Microbiologie pour les Matériaux et l’Environnement, UMR 7564 CNRS, Université de Lorraine, 405 rue de Vandoeuvre, F-54600 Villers-lès-Nancy, France
*
Author to whom correspondence should be addressed.
Current address: Intel Corporation, 4500 S Dobson Road, Chandler, AZ 85248, USA.
Inorganics 2019, 7(2), 15; https://doi.org/10.3390/inorganics7020015
Received: 12 November 2018 / Revised: 11 January 2019 / Accepted: 27 January 2019 / Published: 2 February 2019
(This article belongs to the Special Issue Polyoxometalate Chemistry)
We present the synthesis and structural characterization of the manganese-containing polyoxotungstate, [(Mn(H2O)3)2(H2W12O42)]6− (1), obtained by reaction of MnCl2 with six equivalents of Na2WO4 in the presence of Zn(CH3COO)2 in acetate medium (pH 4.7). This has been assessed by various techniques (FTIR, TGA, UV-Visible, XPS, elemental analysis, single crystal X-ray and electrochemistry). Single-crystal X-ray analyses showed that, in the solid state, 1 forms a 2-D network in which [H2W12O42]10− fragments are linked in pairs via Mn2+ ions, leading to linear chains of the form [(Mn(H2O)3)2(H2W12O42)]n6n. The connection between chains occurs also via Mn2+ ions which bind [H2W12O42]10− fragments belonging to two adjacent chains, forming an infinite 2-D network. A complete electrochemical study was done in aqueous solution where 1 is stable in the pH range 1 to 6. This complex undergoes multiple electron-transfer processes that lead to the electro-generation of manganese high oxidation state species that catalyse water electro-oxidation. 1 is also effective in the electro-catalytic reduction of nitrite and dioxygen. View Full-Text
Keywords: polyoxometalates; manganese; X-ray structure; XPS; electrochemistry; electro-catalysis; WOC; O2 reduction; NOx reduction polyoxometalates; manganese; X-ray structure; XPS; electrochemistry; electro-catalysis; WOC; O2 reduction; NOx reduction
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Teillout, A.-L.; de Oliveira, P.; Marrot, J.; Howell, R.C.; Vilà, N.; Walcarius, A.; Mbomekallé, I.M. Synthesis, Crystal Structure, Electrochemistry and Electro-Catalytic Properties of the Manganese-Containing Polyoxotungstate, [(Mn(H2O)3)2(H2W12O42)]6−. Inorganics 2019, 7, 15.

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