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Issue 26, 2011
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Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal–organic framework

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Abstract

HKUST-1 is one of the popular metal–organic frameworks (MOFs). The formation of this MOF is significantly accelerated by adding Keggin polyoxometalate anions to the synthesis solution. In this paper the chemistry behind this observation was investigated. Upon addition of Keggin type H3PW12O40 heteropolyacid the speciation of Cu2+ cations in ethanol : H2O mixture drastically changes. Combining EPR and XANES measurements with accurate pH measurements and prediction of Cu2+ hydrolysis provides strong evidence for surface induced hydrolysis and consequent dimerisation of monomeric Cu2+ species on Keggin ions in acidic conditions. This enables paddle wheel formation, hence explaining the instantaneous precipitation of Cu3(BTC)2 at room temperature and the systematic encapsulation of Keggin ions in its pores.

Graphical abstract: Effect of Keggin polyoxometalate on Cu(ii) speciation and its role in the assembly of Cu3(BTC)2 metal–organic framework

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Publication details

The article was received on 04 Mar 2011, accepted on 05 May 2011 and first published on 03 Jun 2011


Article type: Paper
DOI: 10.1039/C1JM10947B
J. Mater. Chem., 2011,21, 9768-9771

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    Effect of Keggin polyoxometalate on Cu(II) speciation and its role in the assembly of Cu3(BTC)2 metal–organic framework

    S. R. Bajpe, E. Breynaert, D. Mustafa, M. Jobbágy, A. Maes, J. A. Martens and C. E.A. Kirschhock, J. Mater. Chem., 2011, 21, 9768
    DOI: 10.1039/C1JM10947B

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