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Synthesis and characterization of 0D–3D copper-containing tungstobismuthates obtained from the lacunary precursor Na$_9$[B-$\alpha$-BiW$_9$O$_{33}$]


von Allmen, Kim D; Grundmann, Henrik; Linden, Anthony; Patzke, Greta R (2017). Synthesis and characterization of 0D–3D copper-containing tungstobismuthates obtained from the lacunary precursor Na$_9$[B-$\alpha$-BiW$_9$O$_{33}$]. Inorganic Chemistry, 56(1):327-335.

Abstract

The reaction of the lacunary polyoxometalate precursor Na$_9$[B-$\alpha$-BiW$_9$O$_{33}$]·19.5H$_2$O with Cu(II) ions was explored in search of new economic ways to copper tungstobismuthates as interesting prototypes for water oxidation and reduction catalysts. The emerging series of new 0D–3D polyoxometalate architectures with distinct copper cores was structurally characterized. Na$_6$Rb$_6$[Cu$_3$(H$_2$O)$_3$(BiW$_9$O$_{33}$)$_2$] (Cu-4) and 3D-K$_{6.56}$Cu$_{0.43}$H$_{2.20}$[(Cu$_3$Cl)(K$_{2.62}$Cu$_{0.38}$(H$_2$O)$_3$)(B-$\alpha$-BiW$_9$O$_{33}$)$_2$]·13H$_2$O (Cu-5) display a Cu$_3$(H$_2$O)$_3$ core. The 2D representatives Na$_{12}$[Cu$_2$(H$_2$O)$_4$Cl$_2$(BiW$_{10}$O$_{35}$)$_2$] (Cu-1a), Na$_{10}$[Cu$_2$(H$_2$O)$_6$(BiW$_{10}$O$_{35}$)$_2$] (Cu-1b), 2D-Na$_7$K$_3$Cu$_{0.5}$Cl[Cu$_2$(H$_2$O)$_4$(BiW$_{10}$O$_{35}$)$_2$] (Cu-2), and 2D-Na$_{5.5}$K$_{2.5}$Cu[Cu$_2$(H$_2$O)$_4$(BiW$_{10}$O$_{35}$)$_2$] (Cu-3) contain Cu$_2$(H$_2$O)$_n$W$_2$O$_4$ cores. Interestingly, the bismuth-free 1D paratungstate B Na$_4$K$_4$Cu[H$_2$W$_{12}$O$_{42}$] (Cu-6) is formed through reassembly of the precursor. Cu-5 displays a disordered transition metal core, implying the presence of the polyanions [Cu$_4$(H$_2$O)$_4$(BiW$_9$O$_{33}$)$_2$]$^{10}$– and [Cu$_5$(H$_2$O)$_5$(BiW$_9$O$_{33}$)$_2$]$^8$–. The magnetic properties of Cu-5 as well as its activity as visible-light-driven H$_2$ and O$_2$ evolution catalyst were evaluated.

Abstract

The reaction of the lacunary polyoxometalate precursor Na$_9$[B-$\alpha$-BiW$_9$O$_{33}$]·19.5H$_2$O with Cu(II) ions was explored in search of new economic ways to copper tungstobismuthates as interesting prototypes for water oxidation and reduction catalysts. The emerging series of new 0D–3D polyoxometalate architectures with distinct copper cores was structurally characterized. Na$_6$Rb$_6$[Cu$_3$(H$_2$O)$_3$(BiW$_9$O$_{33}$)$_2$] (Cu-4) and 3D-K$_{6.56}$Cu$_{0.43}$H$_{2.20}$[(Cu$_3$Cl)(K$_{2.62}$Cu$_{0.38}$(H$_2$O)$_3$)(B-$\alpha$-BiW$_9$O$_{33}$)$_2$]·13H$_2$O (Cu-5) display a Cu$_3$(H$_2$O)$_3$ core. The 2D representatives Na$_{12}$[Cu$_2$(H$_2$O)$_4$Cl$_2$(BiW$_{10}$O$_{35}$)$_2$] (Cu-1a), Na$_{10}$[Cu$_2$(H$_2$O)$_6$(BiW$_{10}$O$_{35}$)$_2$] (Cu-1b), 2D-Na$_7$K$_3$Cu$_{0.5}$Cl[Cu$_2$(H$_2$O)$_4$(BiW$_{10}$O$_{35}$)$_2$] (Cu-2), and 2D-Na$_{5.5}$K$_{2.5}$Cu[Cu$_2$(H$_2$O)$_4$(BiW$_{10}$O$_{35}$)$_2$] (Cu-3) contain Cu$_2$(H$_2$O)$_n$W$_2$O$_4$ cores. Interestingly, the bismuth-free 1D paratungstate B Na$_4$K$_4$Cu[H$_2$W$_{12}$O$_{42}$] (Cu-6) is formed through reassembly of the precursor. Cu-5 displays a disordered transition metal core, implying the presence of the polyanions [Cu$_4$(H$_2$O)$_4$(BiW$_9$O$_{33}$)$_2$]$^{10}$– and [Cu$_5$(H$_2$O)$_5$(BiW$_9$O$_{33}$)$_2$]$^8$–. The magnetic properties of Cu-5 as well as its activity as visible-light-driven H$_2$ and O$_2$ evolution catalyst were evaluated.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
07 Faculty of Science > Physics Institute
08 University Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2017
Deposited On:30 Jan 2017 11:42
Last Modified:31 May 2017 07:00
Publisher:American Chemical Society (ACS)
ISSN:0020-1669
Publisher DOI:https://doi.org/10.1021/acs.inorgchem.6b02217
PubMed ID:28001389

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