[BMIM][X] Ionic Liquids Supported on a Pillared-Layered Metal-Organic Framework: Synthesis, Characterization, and Adsorption Properties

Molecules. 2024 Aug 1;29(15):3644. doi: 10.3390/molecules29153644.

Abstract

Combining ionic liquids (ILs) and metal-organic frameworks (MOFs) can be an intriguing opportunity to develop advanced materials with different adsorption capabilities for environmental applications. This study reports the preparation and characterization of a 3D pillared-layered compound, namely, [Zn2(tz)2(bdc)] (CIM91), formed by 1,2,4-triazole (Htz) and 1,4-benzenedicarboxylic acid (H2bdc) ligands. Then, various loadings of the water-stable and hydrophobic IL, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and the water-soluble 1-n-butyl-3-methylimidazolium chloride ([BMIM][Cl]) were incorporated into CIM91. Detailed characterization by X-ray powder diffraction (XRD), FT-IR spectra, scanning electron microscopy (SEM), Energy dispersive X-ray (EDX) analysis, N2 adsorption measurements, and thermogravimetric analysis confirmed the formation of [BMIM][X]/CIM91 composites and the structural stability of the MOF after the incorporation of the ionic liquids. CO2 adsorption-desorption analysis was experimentally carried out for all the materials at 298 K and 318 K, demonstrating a great enhancement in the CO2 adsorption properties of the sole MOF CIM91, particularly by including [BMIM][PF6] species in its structure with a double isosteric heat of CO2 adsorption. The composites were also tested for the adsorption of methylene blue (MB) dye. The results indicate that the incorporation of [BMIM][X] into CIM91 can substantially modify the adsorption properties of the MOF. The influence of the nature of the [BMIM][X] anions on these properties has also been analyzed.

Keywords: composite compounds; ionic liquids; metal–organic framework; pillared-layered frameworks.