Incorporation Of Ionic Liquid Research Articles

Fast and Selective Adsorption of Methylene Blue from Water Using [BMIM][PF6]-Incorporated UiO-66 and NH2-UiO-66

Incorporation of ionic liquids (ILs) into metal–organic frameworks (MOFs) offers a broad potential in various applications. However, their applications in wastewater treatment have remained unexplo...

Characterization of Ethylene-propylene Composites Filled with Perlite and Vermiculite Minerals: Mechanical, Barrier, and Flammability Properties.

Perlite and vermiculite are naturally occurring minerals, commonly used by industry to obtain highly thermoisolative and/or non-flammable materials. However, there has been little research into the preparation and application of rubber compounds containing these inexpensive mineral fillers. Here, we show the benefits of perlite and vermiculite minerals as fillers for ethylene-propylene rubber (EPM) composites. To obtain more uniform dispersion and improved compatibility between the minerals and the elastomer matrix, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (AMIMTFSI) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIMTFSI) imidazolium ionic liquids (ILs) were added. The mineral fillers were found to be attractive semi-reinforcing fillers, which also act as flame retardants in the elastomer composites. Furthermore, a higher content of vermiculite mineral significantly reduced the air permeability of the composites. The incorporation of ionic liquids into the EPM-filled systems had a considerable effect on the torque increment, crosslink density, and more importantly the flammability of the studied compounds. The application of 2.5 parts per hundred parts of rubber (phr) BMIMTFSI, in particular, reduced the flammability of the EPM composite, as the maximum heat release rate (HRRmax) decreased from 189.7 kW/m2 to 170.2 kW/m2.

Bacterial nanocellulose membranes loaded with vitamin B-based ionic liquids for dermal care applications

The development of innovative bio-based skin care products has received an increased attention in the latter years. In the present work, the synthesis of original active principle ingredients based on ionic liquids (ILs) with cholinium cation and vitamins B anions, followed by their incorporation in bacterial nanocellulose (BC) membranes for topical applications, is reported. Three ILs, namely cholinium nicotinate [Ch][B3], cholinium pantothenate [Ch][B5] and cholinium pyridoxylate [Ch][B6], were synthesized through a metathesis reaction and their structure characterized in detail. Thermal analysis confirmed their denomination as ILs and their high thermal resistance. The solubility of these ILs was higher than their vitamin precursors, especially in the case of [Ch][B3] whose solubility increased 30.6-fold enhancing the bioavailability of this vitamin. The incorporation of ILs in BC led to translucent and homogeneous membranes stable up to 190 °C. ILs acted as plasticizers reducing BC brittleness that facilitated their application on irregular skin regions. Moreover, the re-hydration ability of BC-ILs membranes was improved 2.9 to 4.8-fold in comparison to BC, ensuring adequate hydration for ILs release, while the release of ILs in buffer solutions was more complete and faster than the release of vitamins. Finally, BC-ILs were proven not cytotoxic to skin epithelial cells and thus are suitable materials for skin care applications.

Probing the ionic transport dynamics in ionic liquid incorporated CuBTC-Metal-Organic Framework based PVdF-HFP nanocomposite membranes

CuBTC-Metal-Organic Framework (MOF) has been prepared by solvothermal synthesis method and ionic liquid (IL) 1-butyl-3 methylimidazolium tetrafluoroborate (BMIMBF4) has been incorporated at different wt% into the CuBTC-MOF. The composite nanofiller has been dispersed in poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) polymer electrolyte system. Shifting of FTIR vibrational modes of carboxylate group is due to metal-ligand bond elongation upon interaction of ions of IL with CuBTC-MOF. The binding energy of Cu spin-orbit peak increases with incorporation of IL as obtained from XPS spectra suggesting motion of BF4− anions of IL towards the Cu metal nodes of MOF. Periodic oscillation and coordination structure of Cu K-edge are observed in k-space and R-space scanning EXAFS data. Non-Debye dielectric relaxation dynamics is observed from dielectric permittivity and modulus spectra with ionic conductivity of 8.7 × 10−3 Scm−1at 50 wt% of IL incorporation in the composite polymer electrolyte at 380 K. The electrochemical stability profile increases with increasing IL concentration and attains 6.1 V at 50 wt% of IL.

Tuning Water Networks via Ionic Liquid/Water Mixtures.

Water in nanoconfinement is ubiquitous in biological systems and membrane materials, with altered properties that significantly influence the surrounding system. In this work, we show how ionic liquid (IL)/water mixtures can be tuned to create water environments that resemble nanoconfined systems. We utilize molecular dynamics simulations employing ab initio force fields to extensively characterize the water structure within five different IL/water mixtures: [BMIM][BF], [BMIM][PF], [BMIM][OTf], [BMIM][NO] and [BMIM][TFSI] ILs at varying water fraction. We characterize water clustering, hydrogen bonding, water orientation, pairwise correlation functions and percolation networks as a function of water content and IL type. The nature of the water nanostructure is significantly tuned by changing the hydrophobicity of the IL and sensitively depends on water content. In hydrophobic ILs such as [BMIM][PF], significant water clustering leads to dynamic formation of water pockets that can appear similar to those formed within reverse micelles. Furthermore, rotational relaxation times of water molecules in supersaturated hydrophobic IL/water mixtures indicate the close-connection with nanoconfined systems, as they are quantitatively similar to water relaxation in previously characterized lyotropic liquid crystals. We expect that this physical insight will lead to better design principles for incorporation of ILs into membrane materials to tune water nanostructure.

High-conductivity microfiltration membranes incorporated with ionic liquids and their superior anti-fouling effectiveness

Electric membrane bioreactor (E-MBR) for wastewater treatment and water purification has attracted significant interest due to its remarkable performance in fouling mitigation. The performance is much relevant to the electric and physicochemical properties of the conductive membranes in E-MBR. This study proposed a facile method to prepare a conductive membrane with low electrical resistance and enhanced hydrophilicity. Oxidative polymerization of pyrrole doping with ionic liquids was conducted on the surface of polyvinylidene fluoride (PVDF) membranes. Among the studied ionic liquids, 1-butyl-3-vinylimidazolium tetrafluoroborate (BVIMBF4) was the most suitable in this work. The electrical resistance of the PVDF membrane modified by pyrrole and BVIMBF4 (PPy-BVIMBF4/PVDF membrane) was as low as 9.76 Ω/sq, and its water contact angle reduced from 81° to 45°. In the fast-filtration tests, these conductive microfiltration membranes exhibited high rejections of Cu2+ ions (~85%) and Ni+ ions (~65%) and enhanced antifouling performance during the bovine serum albumin filtration with the application of an electric field. A long-term E-MBR operation demonstrated that the transmembrane pressure (TMP) rise and the flux decline of the PPy-BVIMBF4/PVDF membrane were significantly alleviated due to its improved conductivity and hydrophilicity. Its total membrane resistance for water transport was only 27% of the base PVDF membranes under a minute electric field of 0.8 V/m. Overall, the incorporation of ionic liquids in the oxidative polymerization of pyrrole offers a novel and effective strategy in conductive membrane fabrication and serves as an excellent method in fouling mitigation in MBR.

A computational study to design zeolite-templated carbon materials with high performance for CO2/N2 separation

Abstract A comprehensive computational study was performed to develop zeolite-templated carbon (ZTC) materials for efficient carbon dioxide (CO2) and nitrogen (N2) separation. From the previously reported ZTC structure library, our screening based on the grand canonical Monte Carlo simulations identified the types of top ZTCs having high selectivity ( S C O 2 / N 2 ) of CO2 over N2. A detailed investigation about pore structure-property relationship elucidated that high S C O 2 / N 2 is attributed to the strong confinement effect on CO2 gas molecules in small pores. Furthermore, with an attempt to further improve S C O 2 / N 2 , we investigated two approaches which are nitrogen doping and ionic liquid incorporation. Our simulations predicted that nitrogen-doped or ionic liquid incorporated ZTCs exhibited enhanced S C O 2 / N 2 , due to strong interaction between CO2 and negatively charged nitrogen atom or anions in ionic liquid, respectively. While both approaches have provided promises in upgrading ZTCs for high S C O 2 / N 2 , observation of the exceptional cases which showed insignificant changes in S C O 2 / N 2 suggested that design strategy might be altered in accordance with the structural feature of ZTC, representatively, pore topology. Our case study for ZTC-IRR demonstrates that a strategy devised with a deep understanding of pore topology can significantly improve S C O 2 / N 2 of ZTC.

Ionic Liquid Functionalized 3D Mesoporous FDU-12 for Effective SO2 Capture

The emission of SO2 from the combustion of fossil fuels leads to many environmental issues. The incorporation of ionic liquids (ILs) on porous supports to produce supported ionic liquids is an effe...

Investigation of Ionic Liquid interaction with ZnBDC-Metal Organic Framework through Scanning EXAFS and Inelastic Neutron Scattering

Zn based Metal-Organic Framework (MOF), Zinc 1,4-benzenedicarboxylate (ZnBDC) has been synthesized and incorporated with ionic liquid (IL) 1-butyl-3 methylimidazolium bromide (BMIMBr) at optimum 50 wt% of IL. Interaction of BMIMBr in the micropores of ZnBDC-MOF is investigated by XPS, scanning EXAFS and inelastic neutron spectroscopy. Significant increase in binding energies of Zn spin-orbit peaks upon IL incorporation is observed from XPS spectra indicating motion of Br− anions of the IL BMIMBr towards the unsaturated Zn cluster of ZnBDC-MOF. The k-space periodicity as well as the local coordination geometry of Zn K-edge is investigated from the scanning EXAFS and XANES spectra. Asymmetric oscillation periodicity has been observed from the k-space scanning XANES spectra upon IL incorporation. Difference in peak positions of oxygen and zinc are observed from the R-space scanning EXAFS spectra suggesting change in coordination geometry due to dehydration of Zn2+ ion in the ZnBDC-MOF upon IL incorporation. Incorporation of IL in the pores of ZnBDC-MOF gives rise to increased scattering intensity in the Inelastic Neutron Scattering (INS) spectra, which is attributed to the displacement of IL ions in the MOF pores.

Highly Sensitive Humidity Sensor Based on Ionic Liquid–Polymer Composites

Polymer composites comprising the ionic liquid (IL) [Bmim][FeCl4] and poly(vinylidene fluoride) (PVDF) have been developed for humidity sensing applications. Different IL contents (5, 10, and 20 wt %) were incorporated into the PVDF matrix and the morphological, physical–chemical and electrical properties of the composites evaluated, together with their humidity sensitivity response. Higher IL contents (20 wt %) induce a porous morphology in the composites. Further, IL incorporation leads to the crystallization of PVDF in the electroactive β phase, which content increases with the incorporation of IL into the polymer. The thermal stability of the composites decreases with increasing IL content. The humidity sensing response of the composites was evaluated with relative humidity variations from 35 to 90%. It is shown that all composites exhibit a linear resistance variation with the relative humidity, the sensitivity to humidity variations increasing linearly with the IL content. The developed materials show a strong potentiality for printable humidity sensors.

Development of Poly (vinylidene fluoride) and Polyaniline blend with high dielectric permittivity, excellent electromagnetic shielding effectiveness and Ultra low optical energy band gap: Effect of ionic liquid and temperature

Electrically conductive polymer blends have attracted profound attention as dielectric materials. However, achieving isotropic behavior, electrical stability and low current leakage is still challenging. Here we have synthesized a conductive polymer blend of Polyaniline (PANI) and Poly (vinylidene fluoride) (PVDF) exhibiting relatively high dielectric permittivity (εʹ) together with low band gap. Ionic liquid (IL) has been incorporated and the effect of IL in the dielectric properties are explored. The interfacial adhesion, morphology and the dielectric polarization of the blends are investigated. The electromagnetic shielding effectiveness (EMISE) of the conductive blends is studied in X-band frequency range. The electrical stability and decrease in current loss of the blends has been analyzed through I–V characteristics. The findings reveal that with increase in PANI loading in the temperature range of 25–100 °C and IL incorporation results in excellent dielectric properties for charge storage applications. The high efficiency of absorption and low transmission of electromagnetic radiation by the conductive blends is the main reason for excellent EMISE possessed by the systems which can be used for shielding applications in electronics. The increase in electrical stability and decrease in current leakage ability appear in the form of narrow band gap.

Effect of ionic liquid on the structure and desalination performance of PVDF‐PTFE electrospun membrane

ABSTRACTThe relatively large pore size of electrospun membranes might limit their application for direct contact membrane distillation (DCMD). Incorporation of ionic liquid is a potential approach to decrease the pore size of electrospun membranes, which was attributed to the increased conductivity of electrospinning solution. In this study, a novel nanofibrous membrane based on the blends of poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene (PTFE) and ionic liquid (BMIMPF6) was fabricated and applied for the DCMD. The effects of the BMIMPF6 on the morphology, pore size and DCMD performance of the PVDF‐PTFE nanofibrous membrane were investigated. Compared with neat (PVDF‐PTFE) membranes (average pore size: 0.93 μm), the incorporation of BMIMPF6 resulted in a smaller mean pore diameter (0.58 μm). The liquid entry pressure value of the modified composite membrane also increased from 62.75 kPa (neat) to 83 kPa, due to the decreased pore size. The composite membrane exhibited a longer lifespan (about 26 h) than neat membrane during long‐term DCMD process, which makes this composite membrane a promising candidate for DCMD application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48467.

Preparation of a Cross-Linked Sulfonated Poly(arylene ether ketone) Proton Exchange Membrane with Enhanced Proton Conductivity and Methanol Resistance by Introducing an Ionic Liquid-Impregnated Metal Organic Framework.

A novel ionic liquid-impregnated metal-organic-framework (IL@NH2-MIL-101) was prepared and introduced into sulfonated poly(arylene ether ketone) with pendent carboxyl groups (SPAEK) as the nanofiller for achieving hybrid proton exchange membranes. The nanofiller was anchored in the polymeric matrix by the formation of amido linkage between the pendent carboxyl group attached to the molecule chain of SPAEK and amino group belonging to the inorganic framework, thus leading to the enhancement in mechanical properties and dimensional stability. Besides, the hybrid membrane (IL@MOF-1) exhibits an enhanced proton conductivity up to 0.184 S·cm-1 because of the incorporation of ionic liquid in the nanocages of NH2-MIL-101. Moreover, the special structure of NH2-MIL-101 contributes to a low leakage of ionic liquid so as to retain the stable proton conductivity of hybrid membranes under fully hydrated conditions. Furthermore, as a result of a cross-linked structure formed by inorganic nanofiller, the IL@MOF-1 hybrid membrane shows a lower methanol permeability (7.53 × 10-7 cm2 s-1) and superior selectivity (2.44 × 105 S s cm-3) than the pristine SPAEK membrane. Especially, IL@MOF-1 performs high single-cell efficiency with a peak power density of 37.5 mW cm-2, almost 2.3-fold to SPAEK. Electrochemical impedance spectroscopy and scanning electron microscopy indicated that the nanofiller not only contributed to faster proton transfer but also resulted in a tighter bond between the membrane and catalyst. Therefore, the incorporation of IL@NH2-MIL-101 to prepare the hybrid membrane is proven to be suitable for application in direct methanol fuel cells.

Ionic liquid-incorporated polymeric nanoparticles as carriers for prevention and at an earlier stage of periodontal disease

Periodontal diseases are refractory conditions due to difficulty of removal of biofilm and treating inflammation of periodontal region. We therefore focused on prevention of the periodontal diseases and treating at an earlier stage of the periodontal diseases using drug delivery system by removal of biofilm. In the present study, we developed a drug delivery system comprising ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) incorporated and chitosan-modified polymeric nanoparticles using base materials such as poly (DL-lactide-co-glycolide) (PLGA) and polyvinyl caprolactam – polyvinyl acetate – polyethylene glycol graft copolymer (Soluplus®, Sol). The physicochemical and antibacterial properties, cytotoxicity, morphology of the three types of IL-incorporated polymeric nanoparticles were examined. Additionally, retention ability in the periodontal tissue was determined for the case of treatment in the presence of saliva. Our results indicated that IL-incorporated and chitosan-modified Sol nanoparticles showed the highest antibacterial activity against biofilm bacterial cells, with low cytotoxicity. Electron microscopy imaging revealed that the three types of IL-incorporated and chitosan-modified polymeric nanoparticles had differing antibacterial activities in the micro- and nanoscale. Specifically, retention of polymeric nanoparticles in the periodontal tissue of mice was enhanced following IL incorporation. The use of IL for the preparation of polymeric nanoparticles effectively enhanced their antibacterial activity and retention effect, even in the absence of incorporated drug and can apply for prevention and early treatment of periodontal disease.

Green Synthesis of [EMIm]Ac Ionic Liquid for Plasticizing MC-based Biopolymer Electrolyte Membranes

Lithium-ion batteries (LIBs) are favorable power source devices at the last two decades, owing to high energy density, rechargeable, long life cycle, portable, safe, rechargeable, good performance and friendly environment. To support their development, in this research has been successfully prepared polymer electrolyte membrane, a main component of LIBs, based on 1-ethyl-3-methylimidazolium acetate ([EMIm]Ac) ionic liquid-plasticized methyl cellulose/lithium perchlorate (MC/LiClO4). [EMIm]Ac ionic liquid was easy synthesized by metathesis reaction between 1-ethyl-3-methylimidazolium bromide ([EMIm]Br) ionic liquid and potassium acetate (CH3COOK) at ambient temperature, for 1 hour. [EMIm]Ac ionic liquid was functional groups analyzed with Fourier Transform Infra-red (FT-IR) and structural analyzed with 1H-Nuclear Magnetic Resonance (NMR) and 13C-NMR. [EMIm]Ac ionic liquid-plasticized MC/LiClO4 biopolymer electrolyte membrane was prepared by casting solution, with [EMIm]Ac ionic liquid content, 0, 5, 10, 15, 20, 25, and 30% (w/w). Effect of 15% (w/w) [EMIm]Ac ionic liquid incorporation to MC/LiClO4 showed the best condition and selected as the optimum condition with conductivity, tensile strength, elongation break, and thermal stability of 9.160×10-3 S.cm-1, 24.19 MPa, 36.43%, ~256 and ~370 ºC, respectively. These results confirm that [EMIm]Ac ionic liquid can plasticize biopolymer electrolyte membranes of MC/LiClO4 to be appealing performances to fulfill the LIB’s separator requirement. Copyright © 2019 BCREC Group. All rights reserved

Improving CO2 Separation Performance of MIL-53(Al) by Incorporating 1-n-Butyl-3-Methylimidazolium Methyl Sulfate.

1‐n‐Butyl‐3‐methylimidazolium methyl sulfate is incorporated into MIL‐53(Al). Detailed characterization is done by X‐ray fluorescence, Brunauer–Emmett–Teller surface area, scanning electron microscopy, X‐ray diffraction, Fourier‐transform infrared spectroscopy, and thermogravimetric analysis. Results show that ionic liquid (IL) interacts directly with the framework, significantly modifying the electronic environment of MIL‐53(Al). Based on the volumetric gas adsorption measurements, CO2, CH4, and N2 adsorption capacities decreased from 112.0, 46.4, and 19.6 cc (STP) gMIL‐53(Al) −1 to 42.2, 13.0, and 4.3 cc (STP) gMIL‐53(Al) −1 at 5 bar, respectively, upon IL incorporation. Data show that this postsynthesis modification leads to more than two and threefold increase in the ideal selectivity for CO2 over CH4 and N2 separations, respectively, as compared with pristine MIL‐53(Al). The isosteric heat of adsorption (Qst) values show that IL incorporation increases CO2 affinity and decreases CH4 and N2 affinities. Cycling adsorption–desorption measurements show that the composite could be regenerated with almost no decrease in the CO2 adsorption capacity for six cycles and confirm the lack of any significant IL leaching. The results offer MIL‐53(Al) as an excellent platform for the development of a new class of IL/MOF composites with exceptional performance for CO2 separation.

100 MeV O7+ ion irradiation induced electrochemical enhancement in NiBTC metal-organic framework based composite polymer electrolytes incorporated with ionic liquid

Nickel 1,3,5-benzenetricarboxylate (NiBTC) metal-organic framework (MOF), has been synthesized by solvothermal method and dispersed in Poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) polymer. The composite polymer electrolyte membranes were irradiated with 100 MeV O7+ swift heavy ion (SHI) at different fluences and ionic liquid (IL) BMIMBF4 has been incorporated after irradiation. Increasing % uptake of IL has been observed upon IL incorporation as SHI irradiation can enlarge the micropore volumes of NiBTC-MOF by inducing missing linker defects. FTIR spectra depict shifting of carboxylate vibrational modes with increasing fluence suggesting elongation of metal-linker molecular bonds in NiBTC-MOF due to interaction of BF4- anion of IL with unsaturated Ni metal nodes with increasing uptake of IL. Non-Debye relaxation ion dynamics has been revealed from dielectric modulus spectra and optimum ionic conductivity of 9.9 × 10−3 Scm−1 is achieved for the nanocomposite membrane at the fluence of 3.3 × 1012 ions cm−2 at 380 K. The frequency dependent AC conductivity increases with increasing fluence due to higher IL uptake as well as chain scission of the polymer segments. The electrochemical stability of the nanocomposite membrane increases with increasing fluence and attains a maximum value of 6.1 V at 3.3 × 1012 ions cm−2.

An Amphiphilic Mesoporous Polymer Comprising a “built‐in” Imidazolium Ionic Liquid via Nanocasting Method as a Novel Catalyst Support with Combined Prospects

AbstractAn imidazolium based ionic liquid bearing triethylene glycol (TEG) tag was employed as a functional monomer together with divinylbenzene to prepare a novel hydrophilic mesoporous polymer containing ionic liquid functionalities via nanocasting method using SBA‐15 as a hard template. The material was characterized using transmission electron microscopy (TEM), N2 sorption analysis, thermo‐gravimetric analysis (TGA), Fourier‐transform infrared spectroscopy (FT‐IR), elemental analysis (CHN), solid‐state NMR spectroscopy and contact angle measurement. It was found that the hydrophobic/hydrophilic properties of initial template, stepwise addition of monomers and initiator as well as amount of carrier solvent are of the important parameters in preparation of the polymer with uniform pore structure. Benefited from the combined properties such as incorporation of ionic liquid within the pore system of a flexible organic matrix together with its hydrophilic character, the material was found as an appropriate support to generate highly dispersed and very small size of Pd nanoparticles inside the pores. The prepared catalyst in this way, demonstrated outstanding activity, recyclability and high durability in the Suzuki cross‐coupling reaction of varied aryl halides with boronic acids in water as a green reaction medium. The beneficial role of imidazolium ionic liquid in the formation of small and highly active Pd nanoparticles was confirmed with comparative experiments.

Incorporation of Ionic Liquids on Mesoporous Silica Sba-15 as Efficient Sorbents for Co2 Capture Applications

Incorporation of Ionic Liquids on Mesoporous Silica Sba-15 as Efficient Sorbents for Co2 Capture Applications

Flower-like ZnO/ionic liquid composites: structure, morphology, and photocatalytic activity

Two ionic liquids (ILs) with different alkyl chains, 1-butyl-3-methylimidazolium chloride (BMI.Cl) and 1-hexadecyl-3-methylimidazolium chloride (C16MI.Cl), were incorporated into ZnO particles using the microwave-assisted hydrothermal (MAH) method. The morphology and microstructure of ZnO and ZnO/IL composites were characterized along with their photocatalytic effect for dye degradation. While the incorporation of ILs into the ZnO particles did not alter their morphology, it converted the shallow defects into deep defects. These changes improved Rhodamine B (RhB) photodegradation efficiency. The dye degradation reached 62% when ZnO/C1640 was used, whereas it reached 30% when pure ZnO was used, during the same time interval.