A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity.

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Title: A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity.
Authors: Junghans, Ulrike1 ulrike.junghans@uni-leipzig.de, Kobalz, Merten2 merten.kobalz@chemie.uni-leipzig.de, Erhart, Oliver2 O.Erhart@web.de, Preißler, Hannes3 preissler@inc.uni-leipzig.de, Lincke, Jörg2 joerglincke@gmx.de, Möllmer, Jens3 moellmer@inc.uni-leipzig.de, Krautscheid, Harald2 krautscheid@rz.uni-leipzig.de, Gläser, Roger1,3 roger.glaeser@uni-leipzig.de
Source: Materials (1996-1944). Apr2017, Vol. 10 Issue 4, p338. 33p. 2 Diagrams, 8 Charts, 20 Graphs.
Subjects: Robust control, Isomorphous structures, Metal-organic frameworks, Alkyl compounds, Thermal stability
Abstract: The synthesis and characterization of an isomorphous series of copper-containing microporous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula ∞³[Cu4(μ3-OH)2(R¹-R²-trz-ia)3(H2O)x] are presented. Through size adjustment of the alkyl substituents R¹ and/or R² at the linker, the impact of linker functionalization on structure-property relationships was studied. Due to the arrangement of the substituents towards the cavities, the porosity (pore fraction 28%-39%), as well as the pore size can be adjusted by the size of the substituents of the triazole ring. Thermal analysis and temperature-dependent PXRD studies reveal a thermal stability of the MOFs up to 230 °C due to increasing framework stability through fine-tuning of the linker substitution pattern. Adsorption of CO2 (298 K) shows a decreasing maximum loading with increasing steric demand of the substituents of the triazole ring. Furthermore, the selective oxidation of cyclohexene with tert-butyl hydroperoxide (TBHP) is studied over the MOFs at 323 K in liquid chloroform. The catalytic activity increases with the steric demand of the substituents. Additionally, these isomorphous MOFs exhibit considerable robustness under oxidizing conditions confirmed by CO2 adsorption studies, as well as by the catalytic selective oxidation experiments. [ABSTRACT FROM AUTHOR]
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Abstract:The synthesis and characterization of an isomorphous series of copper-containing microporous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula ∞³[Cu4(μ3-OH)2(R¹-R²-trz-ia)3(H2O)x] are presented. Through size adjustment of the alkyl substituents R¹ and/or R² at the linker, the impact of linker functionalization on structure-property relationships was studied. Due to the arrangement of the substituents towards the cavities, the porosity (pore fraction 28%-39%), as well as the pore size can be adjusted by the size of the substituents of the triazole ring. Thermal analysis and temperature-dependent PXRD studies reveal a thermal stability of the MOFs up to 230 °C due to increasing framework stability through fine-tuning of the linker substitution pattern. Adsorption of CO2 (298 K) shows a decreasing maximum loading with increasing steric demand of the substituents of the triazole ring. Furthermore, the selective oxidation of cyclohexene with tert-butyl hydroperoxide (TBHP) is studied over the MOFs at 323 K in liquid chloroform. The catalytic activity increases with the steric demand of the substituents. Additionally, these isomorphous MOFs exhibit considerable robustness under oxidizing conditions confirmed by CO2 adsorption studies, as well as by the catalytic selective oxidation experiments. [ABSTRACT FROM AUTHOR]
ISSN:19961944
DOI:10.3390/ma10040338