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

被引：29

作者：

Bajpe, Sneha R. ^{[1
]}

Breynaert, Eric ^{[1
]}

Mustafa, Danilo ^{[1
]}

Jobbagy, Matias ^{[2
]}

Maes, Andre ^{[1
]}

Martens, Johan A. ^{[1
]}

Kirschhock, Christine E. A. ^{[1
]}

机构：

[1] Katholieke Univ Leuven, Ctr Surface Sci & Catalysis, Dept Microbial & Mol Syst, B-3000 Louvain, Belgium

[2] FCEN UBA, INQUIMAE DQIAQF, Lab Super & Mat Func, Buenos Aires, DF, Argentina

来源：

JOURNAL OF MATERIALS CHEMISTRY | 2011年 / 21卷 / 26期

关键词：

CLUSTERS;

D O I：

10.1039/c1jm10947b

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 Cu-3(BTC)(2) at room temperature and the systematic encapsulation of Keggin ions in its pores.

引用

页码：9768 / 9771

页数：4

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