Synthesis, characterization and evaluation of ionic liquids and polymeric ionic liquids/functionalized multiwalled carbon nanotubes for Cr(VI) adsorption.

Abstract

In this study, a series of imidazolium and pyridinium-based ionic liquids (ILs), polymeric ionic liquids (PILs), and their carbon nanotubes-functionalized composites were synthesized, characterized and applied as potential adsorbents for hexavalent Cr(VI). Polymeric ionic liquids of different polymerizable moieties (vinyl and styrenic moieties) were studied. Furthermore, multi-walled carbon nanotubes (MWCNTs) were synthesized, characterized and dispersed on both imidazolium and pyridinium-based ILs and PILs, respectively. Thermal studies revealed that vinyl pyridinium PILs possess good thermal stability than the vinyl imidazolium counterparts. The size of the counter-anions bromide (Br-), hexafluorophosphate (PF6-), and bis(trifluoromethanesulfonyl) imide (TFSI-) and the charge delocalization in cationic rings greatly influenced the glass transition temperatures of PILs. Expectedly, pyridinium and imidazolium-based PILs with hexafluorophosphate ions showed poor solubility in polar protic solvents (water, methanol) and good solubility in polar aprotic solvents (DMSO, DMF, THF) except acetone (a dipolar aprotic solvent). The as-synthesized ILs/MWCNT composites were characterized using FTIR spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and thermal analysis. The results obtained indicate that the pyridinium-based ILs exhibited higher decomposition temperatures (above 400 °C) compared to imidazolium-based ILs counterparts (onset decomposition at 250 °C) with poor water-solubility and their glass transition temperatures were dependent on ion mobility. The effect of the alkyl lateral chain (propyl and isopropyl) at the first and third position of imidazolium and N-position of pyridinium cationic rings towards their thermal stability, conductivity, and solubility of the ionic liquids was investigated. Their solubilities in different polar and non-polar solvents were also investigated. Spectroscopic and microscopic analyses confirmed the formation of the ILs/MWCNT composites with new functionalities and unaltered surface morphology of carbon nanotubes. Pyridinium and imidazolium-based PILs/MWCNT composites were characterized by thermal, spectroscopic, and electron microscopy techniques. It was observed that the composites were thermally stable compared to the corresponding precursors and were insoluble in polar aprotic solvents. For application, solid-liquid adsorption process was used in the adsorption of Cr(VI) from aqueous solution using the as-synthesized ILs/MWCNT and PILs/MWCNT composites as adsorbents. Under batch adsorption experiments, the effect of solution pH, contact time and initial concentration of Cr(VI) were investigated. It was established that the adsorption of Cr(VI) took place under acidic conditions (pH=2-3), thereby confirming significant adsorption of dichromate (Cr2O7-) and hydrochromate (HCrO4-) anions. At lower pH values, the ionic and π-anionic electrostatic interactions between the positively-charged regions of the composites and Cr(VI) were believed to have facilitated the adsorption of anionic (Cr2O7-) and (HCrO4-). Adsorption results obtained based on contact time showed that increase in contact time gradually increases the adsorption of Cr(VI) within 2 h. However, further increase in experimental contact time above 2 h insignificantly affected the adsorption of Cr(VI) due to early or quick oversaturation of the surface active sites on the adsorbents. The adsorption of Cr(VI) onto ILs/MWCNT and PILs/MWCNT composites fitted well into both Langmuir and Freundlich adsorption isotherms. However, the homogeneity/heterogeneity nature of the adsorbents relied on the diversified nature of the composites, which includes bulky pyridinium and imidazolium organic cations with delocalized charges, some large counter anions and the graphitic functional carbon groups. In order to understand the mechanisms of the adsorption of Cr(VI) onto ILs/MWCNT and PILs/MWCNT composites, pseudo-second-order kinetic model was employed. The results obtained showed that the calculated maximum adsorption capacities (qecal) and experimental maximum adsorption capacities (qe.exp) depict high correlation co-efficiencies (R2>0.99) confirming the applicability and feasibility of pseudo-second-order model on the adsorption of Cr(VI) in this study.