Type 3 porous liquids based on non-ionic liquid phases - a broad and tailorable platform of selective, fluid gas sorbents.
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ABSTRACT:
SUBMITTER: Cahir J
PROVIDER: S-EPMC8150117 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:In this paper, the potential of novel polymer sorbents with the imprinted IL-functional group for the removal of Cu(II), Cd(II), and Zn(II) from aqueous solutions was investigated by batch mode. The sorbents were fabricated by direct reaction of the prepared polymer matrix (poly(vinylbenzyl chloride-divinylbenzene), VBC, and poly(vinylbenzyl bromide-divinylbenzene), VBBr) with 1-(3- or 4-pyridyl)undecan-1-one and oxime of 1-(3- or 4-pyridyl)undecan-1-one. The Fourier Transform Infrared Spectroscopy (FT-IR), Raman Spectroscopy (Raman), Thermogravimetric Analysis (TG), Differential Scanning Calorimetry (DSC), and Scanning Electron Microscopy (SEM) techniques were used to show functionality and stability of the sorbents. The materials were also characterized by contact-angle goniometry, X-rayphotoelectron spectroscopy (XPS), and Zeta potential analysis. The removal of Cd(II), Cu(II), and Zn(II) was monitored and optimized under the influence of several operational controlling conditions and factors such as pH, shaking time, temperature, initial metal ions concentration, and counter-ions at the functional group. The results obtained confirmed the very high potential of the sorbents; however, the properties depend on the structure of the functional group. The tested sorbents showed fast kinetics, significant capacity at 25 °C (84 mg/g for the Zn(II) sorption with VBC-Ox4.10, 63 mg/g for the Cd(II) sorption with VBBr-Ox3.10, and 69 mg/g for the Cu(II) sorption with VBC-K3.10), and temperature dependence (even 100% increase in capacity values at 45 °C). The selected sorbent can be regenerated without a significant decrease in the metal removal efficiency.
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Project description:The effect of confining ionic liquids (ILs) such as 1-ethyl-3-methylimidazolium tetrafluoroborate [C2C1Im][BF4] or 1-butyl-3-methylimidazolium tetrafluoroborate [C4C1Im][BF4] in silica matrices was investigated by high-pressure IR spectroscopy. The samples were prepared via the sol-gel method, and the pressure-dependent changes in the C-H absorption bands were investigated. No appreciable changes were observed in the spectral features when the ILs were confined in silica matrices under ambient pressure. That is, the infrared measurements obtained under ambient pressure were not sufficient to detect the interfacial interactions between the ILs and the porous silica. However, dramatic differences were observed in the spectral features of [C2C1Im][BF4] and [C4C1Im][BF4] in silica matrices under the conditions of high pressures. The surfaces of porous silica appeared to weaken the cation-anion interactions caused by pressure-enhanced interfacial IL-silica interactions. This confinement effect under high pressures was less obvious for [C4C1Im][BF4]. The size of the cations appeared to play a prominent role in the IL-silica systems.
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Project description:The potential applications of cationic poly(ionic liquids) range from medicine to energy storage, and the development of efficient synthetic strategies to target innovative cationic building blocks is an important goal. A post-polymerization click reaction is reported that provides facile access to trisaminocyclopropenium (TAC) ion-functionalized macromolecules of various architectures, which are the first class of polyelectrolytes that bear a formal charge on carbon. Quantitative conversions of polymers comprising pendant or main-chain secondary amines were observed for an array of TAC derivatives in three hours using near equimolar quantities of cyclopropenium chlorides. The resulting TAC polymers are biocompatible and efficient transfection agents. This robust, efficient, and orthogonal click reaction of an ionic liquid, which we term ClickabIL, allows straightforward screening of polymeric TAC derivatives. This platform provides a modular route to synthesize and study various properties of novel TAC-based polymers.
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Project description:Because of the appealing properties, ionic liquids (ILs) are believed to be promising alternatives for the CO2 absorption in the flue gas. Several ILs, such as [NH2emim][BF4], [C4mim][OAc], and [NH2emim[OAc], have been used to capture CO2 of the simulated flue gas in this work. The structural changes of the ILs before and after absorption were also investigated by quantum chemical methods, FTIR, and NMR technologies. However, the experimental results and theoretical calculation showed that the flue gas component SO2 would significantly weaken the CO2 absorption performance of the ILs. SO2 was more likely to react with the active sites of the ILs than CO2. To improve the absorption capacity, the ionic liquid (IL) mixture [C4mim][OAc]/ [NH2emim][BF4] were employed for the CO2 absorption of the flue gas. It is found that the CO2 absorption capacity would be increased by about 25%, even in the presence of SO2. The calculation results suggested that CO2 could not compete with SO2 for reacting with the IL during the absorption process. Nevertheless, SO2 might be first captured by the [NH2emim][BF4] of the IL mixture, and then the [C4mim][OAc] ionic liquid could absorb more CO2 without the interference of SO2.
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Project description:Several synthetic methods have recently emerged to develop high-surface-area solid-state organic framework-based materials into free-flowing liquids with permanent porosity. The fluidity of these porous liquid (PL) materials provides them with advantages in certain storage and transport processes. However, most framework-based materials necessitate the use of cryogenic temperatures to store weakly bound gases such as H2, temperatures where PLs lose their fluidity. Covalent organic framework (COF)-based PLs that could reversibly form stable complexes with H2 near ambient temperatures would represent a promising development for gas storage and transport applications. We report here the development, characterization, and evaluation of a material with these remarkable characteristics based on Cu(I)-loaded COF colloids. Our synthetic strategy required tailoring conditions for growing robust coatings of poly(dimethylsiloxane)-methacrylate (PDMS-MA) around COF colloids using atom transfer radical polymerization (ATRP). We demonstrate exquisite control over the coating thickness on the colloidal COF, quantified by transmission electron microscopy and dynamic light scattering. The coated COF material was then suspended in a liquid polymer matrix to make a PL. CO2 isotherms confirmed that the coating preserved the general porosity of the COF in the free-flowing liquid, while CO sorption measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed the preservation of Cu(I) coordination sites. We then evaluated the gas sorption phenomenon in the Cu(I)-COF-based PLs using DRIFTS and temperature-programmed desorption measurements. In addition to confirming that H2 transport is possible at or near mild refrigeration temperatures with these materials, our observations indicate that H2 diffusion is significantly influenced by the glass-transition temperature of both the coating and the liquid matrix. The latter result underscores an additional potential advantage of PLs in tailoring gas diffusion and storage temperatures through the coating composition.
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