Dopant-Controlled Crystallization in Metal–Organic Frameworks: The Role of Copper(II) in Zinc 1,4-Benzenedicarboxylate

A series of Zn–Cu 1,4-benzenedicarboxylate(bdc) metal organic frameworks(MOF) have been synthesized by introducing N,N -dimethylformamide(DMF) solutions of 1,4-benzenedicarboxylic acid to metal salt solutions with a range of concentrations of Cu(NO3)2 and Zn(NO3)2 across the entire composition range...

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Bibliographic Details
Published in:Journal of physical chemistry. C 2012-07, Vol.116 (29), p.15322-15328
Main Authors: Carson, Cantwell G, Ward, Jason, Liu, Xiao Tao, Schwartz, Justin, Gerhardt, Rosario A, Tannenbaum, Rina
Format: Article
Language:English
Subjects:
Condensed matter: structure, mechanical and thermal properties
Exact sciences and technology
Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals
Physics
Structure of solids and liquids
crystallography
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Summary:A series of Zn–Cu 1,4-benzenedicarboxylate(bdc) metal organic frameworks(MOF) have been synthesized by introducing N,N -dimethylformamide(DMF) solutions of 1,4-benzenedicarboxylic acid to metal salt solutions with a range of concentrations of Cu(NO3)2 and Zn(NO3)2 across the entire composition range. At the Zn-rich side of the range, the presence of Cu(II) had the effect of changing the polymorph of the solid from the predominantly P21/n structure, associated with MOF-2, to the C2/m structure, shared with Cu(bdc). There was an associated change in crystal morphology that accompanied the addition of a Cu salt impurity. BET surface area measurements of the thermally desolvated product showed that the surface area of the Zn(bdc) increased with the addition of Cu. At the Cu-rich side, magnetic susceptibility measurements indicated that the presence of the Zn impurity increased the fraction of paramagnetic Cu centers, suggesting the formation of a large fraction of heterometallic secondary building units(hSBU) in the framework.
ISSN:1932-7447
1932-7455
DOI:10.1021/jp2117032