In Situ X-ray Absorption Spectroscopy Studies of Kinetic Interaction between Platinum(II) Ions and UiO-66 Series Metal–Organic Frameworks

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2014-01-01
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Xiao, Chaoxian
Goh, Tian Wei
Brashler, Kyle
Pei, Yuchen
Guo, Zhiyong
Huang, Wenyu
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Huang, Wenyu
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Ames National LaboratoryChemistry
Abstract

The interaction of guest Pt(II) ions with UiO-66–X (X = NH2, H, NO2, OMe, F) series metal–organic frameworks (MOFs) in aqueous solution was investigated using in situ X-ray absorption spectroscopy. All of these MOFs were found to be able to coordinate with Pt(II) ions. The Pt(II) ions in UiO-66–X MOFs generally coordinate with 1.6–2.4 Cl and 1.4–2.4 N or O atoms. We also studied the time evolution of the coordination structure and found that Pt(II) maintained a coordination number of 4 throughout the whole process. Furthermore, the kinetic parameters of the interaction of Pt(II) ions with UiO-66–X series MOFs (X = NH2, H, NO2, OMe, F) were determined by combinational linear fitting of extended X-ray absorption fine structure (EXAFS) spectra of the samples. The Pt(II) adsorption rate constants were found to be 0.063 h–1 for UiO-66–NH2 and 0.011–0.017 h–1 for other UiO-66–X (X = H, NO2, OMe, F) MOFs, which means that Pt(II) adsorption in UiO-66–NH2 is 4–6 times faster than that in other UiO-66 series MOFs. FTIR studies suggested that the carboxyl groups could be the major host ligands binding with Pt(II) ions in UiO-66 series MOFs, except for UiO-66–NH2, in which amino groups coordinate with Pt(II) ions.

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Reprinted (adapted) with permission from J. Phys. Chem. B, 2014, 118 (49), pp 14168–14176. Copyright 2014 American Chemical Society.

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Wed Jan 01 00:00:00 UTC 2014
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