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Proton and water activity-controlled structure formation in zinc carboxylate-based metal organic frameworks.

The journal of physical chemistry. A (2008-07-26)
Steffen Hausdorf, Jörg Wagler, Regina Mossig, Florian O R L Mertens
ABSTRACT

The contributions of terephthalic acid and Zn(2+)-coordinated water in N,N-diethylformamide (DEF) to the overall proton activity in the synthesis of MOF-5 (Zn4O(BDC)3, BDC = 1,4-benzenedicarboxylate) were quantitatively determined by combined electrochemical and UV-vis spectroscopic measurements. Structural transformations of zinc carboxylate-based metal organic frameworks due to their exposure to environments with variable water concentrations and the chemical means necessary to revert these transitions have been investigated. It was found that the water-induced structural transition of MOF-5 to the hydroxide structure Zn3(OH)2(BDC)2 x 2 DEF (MOF-69c) can be reverted by a thermal treatment of the obtained compound and its subsequent exposure to anhydrous DEF. MOF-5 syntheses from simple carboxylates as well as a water-free synthesis based on nitrate decomposition are presented. The latter demonstrates that nitrate can serve as the sole source for the oxide ion in MOF-5.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Iron(III) oxo acetate perchlorate hydrate
Sigma-Aldrich
Cobalt(II) oxo pivalate

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