Towards complete elucidation of structural factors controlling thermal stability of IL/MOF composites: effects of ligand functionalization on MOFs
- 26 June 2020
- journal article
- research article
- Published by IOP Publishing in Journal of Physics: Condensed Matter
- Vol. 32 (48), 484001
- https://doi.org/10.1088/1361-648x/aba06c
Abstract
In this work, we incorporated an ionic liquid (IL), 1-n-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO4]) into two different metal organic frameworks (MOFs), UiO-66, and its amino-functionalized counterpart, NH2-UiO-66, to investigate the effects of ligand-functionalization on the thermal stability limits of IL/MOF composites. The as-synthesized IL/MOF composites were characterized in detail by combining X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller analysis (BET), X-ray fluorescence (XRF), infrared spectroscopies (FTIR), and their thermal stability limits were determined by thermogravimetric analysis (TGA). Characterization data confirmed the successful incorporation of the IL into each MOF and indicated the presence of direct interactions between them. A comparison of the interactions in [BMIM][MeSO4]-incorporated UiO-66 and NH2-UiO-66 with those in their 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6])-incorporated counterparts showed that the hydrophilic IL, [BMIM][MeSO4], interacts with the 1,4-benzenedicarboxylate (BDC) ligand of the UiO-66, while the hydrophobic IL, [BMIM][PF6], is interacting with the joints where zirconium metal cluster coordinates with BDC ligand. The TGA data demonstrated that the composite with the ligand-functionalized MOF, NH2-UiO-66, exhibited a lower percentage decrease in the maximum tolerable temperature compared to those of IL/UiO-66 composites. Moreover, it is discovered that when the IL is hydrophilic, its hydrogen bonding ability can be utilized to designate an interaction site on MOF's ligand structure which will lead to a lower reduction in thermal stability limits. These results provide insights for the rational design of IL/MOF composites and contribute towards the complete elucidation of structural factors controlling the thermal stability.Keywords
Funding Information
- The Scientific and Technological Research Council of Turkey ((TUBITAK project no. 114R093))
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