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Some embodiments described herein relate to ionic liquids comprising an anion of a heteraromatic compound such as optionally substituted pyrrolide, optionally substituted pyrazolide, optionally substituted indolide, optionally substituted phospholide, or optionally substituted imidazolide. Methods and devices for gas separation or gas absorption related to these ionic liquids are also described herein.
Over the past decade, perovskite photovoltaics have approached other currently available technologies and proven to be the most prospective type of solar cells. Although the many-sided research in this very active field has generated consistent results with regard to their undisputed consistently increasing power conversion efficiency, it also produced several rather contradictory opinions. Among other important details, debate surrounding their proneness to surface degradation and poor mechanical robustness, as well as the environmental footprint of this materials class, remains a moot point. The application of ionic liquids appears as one of the potential remedies to some of these challenges due to their high conductivity, the opportunities for chemical “tuning” of the structure, and relatively lower environmental footprint. This article provides an overview, classification, and applications of ionic liquids in perovskite solar cells. Here, we summarize the use and role of ionic liquids as versatile additives, solvents, and modifiers in perovskite precursor solution, in charge transport layer, and in interfacial and stability engineering. Finally, challenges and the future prospects for the design and/or selection of ionic liquids with a specific profile that meets the requirements for next-generation highly efficient and stable perovskite solar cells are proposed.
Powertrains in electric vehicles are exposed to stray currents that accelerate wear and cause failure of mechanical components. These durability issues are further aggravated when using low-viscosity lubricants, which are desired for energy efficiency but create harsher contact conditions at sliding interfaces. This study investigates a phosphonium phosphate ionic liquid as a performance-enhancing additive in a low-viscosity base oil for lubricating electrified sliding interfaces. Ionic liquids can adsorb and react on contact interfaces via stress-assisted chemical reactions, generating nanometric tribofilms that provide protection against wear. However, the effect of electric fields on the mechanochemistry of ionic liquids is poorly understood, hindering their adoption in lubricants for electrified powertrains. This article reports an in situ optical interferometry study of ionic liquid derived tribofilm growth kinetics at stressed sliding/rolling interfaces under direct currents. The application of electric currents accelerated tribofilm formation up to a critical current density (∼1.4 A/mm 2 ), beyond which pitting-induced wear dominated. The tribofilms were composed of iron phosphates, iron oxides, and carbon species, with iron oxides becoming predominant under applied currents. These tribofilms prevented the scuffing failure of steel surfaces under electrified conditions. Based on the results, a kinetic model is proposed that integrates electric current effect into the classical stress-assisted thermal activation framework to allow prediction of tribofilm growth at electrified sliding contacts. This framework provides crucial guidance for designing next-generation lubricants for electrified transportation and power generation systems.
Electrical double-layer capacitors (EDLCs) are of increasing importance in energy storage from renewable sources. The properties of the electrode and electrolyte materials influence the energy and power densities of EDLCs. We examined the specific capacitance and ion dynamics of a protic ionic liquid confined in pre-intercalated Ti 3 C 2 T x MXene. Our electrochemical measurements demonstrated that the creation of a protic ionic liquid, 1-butyl-3-H-imidazolium bis(trifluoromethanesulfonyl)imide (BuIMH-NTf2), using a mixture of ionic liquid, 1-butyl imidazole (BuIM), and salt, bis(trifluoromethanesulfonyl)imide (HNTf2), in a ratio of 0.8:0.2 led to the optimal capacitance. Remarkably, quasi-elastic neutron scattering measurements revealed increased particle mobility at this composition, attributed to the more efficient accumulation of BuIMH + on the electrode surface. This deposit of additional ions results in fewer BuIM molecules away from the surface, enhancing their mobility due to reduced crowding. This composition-dependent electrochemical behavior will guide the formulation of more efficient protic ionic liquid systems, enabling faster ion transport in energy storage devices.
Oil-soluble ionic liquids (ILs) have been proved as effective additives in lubricant oils through tribological experiments and post-test analytical analyses. Here, surface structures of lubricant base oil, oil-soluble ILs, and their mixtures at the air/liquid and solid/liquid interfaces have been studied using sum frequency generation (SFG) vibrational spectroscopy. At the air/base oil and air/IL interfaces, the alkyl chains of the studied compounds were shown to be conformationally disordered and their terminal methyl groups point outward at the liquid surface. The base oil dominates the air/(base oil + IL) interface due to its higher surface excess propensity and larger bulk concentration. At the solid (silica) surface, ILs adopt a structure with their charged headgroups in contact with the silica surface, while their alkyl chains are more conformationally ordered or packed compared to the air/IL interface. At the interface between silica and (base oil + IL) mixtures, ILs also preferentially adsorb to the silica surface with their layer structures somewhat different from those of ILs alone. These results showed that ILs can adsorb onto the solid surface even before tribological contacts are made. The insights obtained from this SFG study provide a better understanding of the role of ionic liquids in lubrication.
Here, the morphology of DNA is strongly influenced by its surrounding environment, including factors such as pH, salt type and valency, and the presence of polymers. Inorganic salts are known to reduce the DNA chain length through mechanisms like electrostatic screening and ion bridging. In contrast, ionic liquids, a new class of organic salts, have previously been found to increase the DNA chain length, indicating a distinct mode of interaction between the ionic liquid and DNA chains. This study utilizes self-assembled DNA-AuNPs as a model system to examine changes in the DNA chain morphology and the nanoscale interaction mechanisms in an ionic liquid environment. The DNA chain lengths are measured in solution using X-ray scattering measurements at varying concentrations of two imidazolium ([$BMIM$] acetate and [$EMIM$] acetate) based ionic liquids. Additionally, Molecular Dynamics (MD) simulations are performed mimicking the experimental system. Our results suggest an interplay of electrostatic and groove-binding interactions governing the DNA chain morphology, which depends on IL concentration and the composition of the DNA chains. It has been found that for DNA chains with majority ssDNA, electrostatic interaction dominate, however with increasing composition of double strands, the DNA chains exhibit compaction due to a non-electrostatic hydrophobic groove-binding mechanism.
Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.
Poly(norbornene)s and poly(ionic liquid)s are two different classes of attractive materials, which are known for their structural tunability and thermal stabilities, and have been extensively studied as gas separation membranes. The incorporation of ionic liquids (ILs) into the poly(norbornene) through post-polymerization has resulted in unique materials with synergistic properties. However, direct polymerization of norbornene-containing IL monomers as gas separation membranes are limited. To this end, a series of norbornene-containing imidazolium-based mono- and di-cationic ILs (NBM-mIm and NBM-DILs) with different connectivity and spacer lengths were synthesized and characterized spectroscopically. Subsequently, the poly(NBM-mIm) with bistriflimide [Tf2N−] and poly([NBM-DILs][Tf2N]2) comprising homo-, random-, and block- (co)polymers were synthesized via ring-opening metathesis polymerization using the air-stable Grubbs second-generation catalyst. Block copolymers (BCPs), specifically, [NBM-mIM][Tf2N] and [NBM-ImCnmIm] [Tf2N]2 (n = 4 and 6) were synthesized at two different compositions, which generated high molecular weight polymers with decent solubility relative to homo- and random (co)polymers of [NBM-DILs] [Tf2N]2. The prepared BCPs were efficiently analyzed by a host of analytical tools, including 1H-NMR, GPC, and WAXD. The successfully BCPs were cast into thin membranes ranging from 47 to 125 μm and their gas (CO2, N2, CH4, and H2) permeations were measured at 20 °C using a time-lag apparatus. These membranes displayed modest CO2 permeability in a non-linear fashion with respect to composition and a reverse trend in CO2/N2 permselectivity was observed, as a usual trade-off behavior between permeability and permselectivity.
Silicon surfaces with termination of hydrogen (H–Si), quartz, native silicon (native-Si), and chemically deposited (Au–Si) cd and sputtered gold (Au–Si) s were fabricated with roughness less than 6 Å to study the solid–liquid interface of the ionic liquid (IL) methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, [N 1888 ][TFSI], by neutron reflectometry (NR). The modifications made to the silicon surface were to obtain a native positive or negative charge similar to a charged surface in electrochemical systems. The differences in scattering length density (SLD) based on mass density and composition of IL were examined. Perpendicular to the substrate surface, a distinct transition between the first ion layer and the bulk liquid is resolved out of the reflectivity data for the gold surfaces and in particular the chemically deposited Au–Si. Other interfaces are best described by a diffuse transition between regions of different SLDs. The diffuse transitions between SLDs observed here suggest that the interfacial structure of IL, while ordered, is best described by a continuous variation in composition as opposed to distinct layers of ions.
This document is the final report resulting from the work conducted by undergraduate students at the University of South Alabama during the 2018/2019 academic year and was prepared by the undergraduate students. As NASA pushes the boundaries further into space, the current technologies within the various life support systems must be improved upon. One such improvement is needed to the current air revitalization systems, specifically sorbents that can capture CO2 more effectively from enclosed habitats. Ionic liquids (ILs) have been considered as absorbents for flue gas, but little research has been done to test the ability of ILs at ambient pressures and relatively low concentration of CO2. The experiment outlined below utilizes the task-specific ionic liquid, tetramethylammonium taurinate (TMN), in a commercial off the shelf absorption system to capture CO2. The CO2 stream is combined with nitrogen to produce an inlet gas concentration relevant to close air revitalization applications. At an inlet gas flow with a CO2 partial pressure of 3.8 torr the system was capable of removing just under 97% of the inlet CO2. The concentration of CO2 in the outlet stream, partial pressure 0.16 torr, was less than that of atmospheric air. The duty required to separate the absorbed gas from the ionic liquid as well to cool the ionic liquid to be reintroduced to the column were acquired utilizing laboratory cooling/heating baths. These results show that TMN may be an efficient candidate for consideration in closed air revitalization.
Advancing the sustainability of nanoparticle electrocatalyst synthesis requires reducing solvent waste without compromising catalytic performance. Here, we report a rapid, microwave‐assisted colloidal synthesis of NiMo alloy nanoparticles in the ionic liquid 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM‐NTf 2 ), which serves as both reaction medium and recyclable solvent. NiMo nanoparticles with tunable compositions were obtained within 1 min at 230 °C, with Ni 0.86 Mo 0.14 giving the highest activity toward the hydrogen evolution reaction (HER), achieving an onset potential of −129 mV, an overpotential at 10 mA cm −2 of −290 mV versus RHE in acidic electrolyte, and >99% Faradaic efficiency. The ionic liquid was recovered and purified via aqueous NH 4 OH extraction, removing over 99% of residual Mo species, and reused for up to five successive syntheses. Nanoparticles prepared in recycled BMIM‐NTf 2 retained comparable crystallinity, morphology, and catalytic activity, with stable HER performance over 45 h of electrolysis. These results demonstrate that ionic liquid recycling can improve the sustainability of the preparation of NiMo nanoparticle electrocatalysts while preserving performance and material integrity.
This work is focused on advancing of the understanding the carbon dioxide (CO2) sorption characteristics of imidazolium ionic liquid crystals based on the 1-alkyl-3-methylimidazolium (Cnmim) ionic liquid family. Specifically, the mechanism of sorption across the melting, liquid crystal, and isotropic liquid transitions is investigated for 1-tetradecyl-3-methylimidazolium tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-). A unique reversible CO2 occlusion was observed in 1-tetradecyl-3-methylimidazolium tetrafluoroborate (C14mim BF4) under rapid temperature quench from the liquid phases to the solid phase, while complete desorption occurred upon heating above the melting point (40 degrees C). In situ wide-angle x-ray scattering revealed that the lamellar structure of C14mim BF4 liquid crystal phases provides a high concentration of dynamically accessible anion and cation interaction sites for CO2, facilitating CO2 occlusion upon rapid solidification. The selective occlusion of CO2 in C14mim BF4 suggests a new mechanism for CO2 sorption processes.
There is increasing interest in studying molecular motions in ionic liquids to gain better insights into their transport properties and to expand their applications. Here, in this study, we have employed the fast field cycling relaxometry and pulsed field gradient nuclear magnetic resonance techniques to investigate the rotational and translational dynamics of fluorinated imide-based ionic liquids (ILs) at different temperatures. We have studied a total of six ILs composed of the 1-butyl-3-methylimidazolium cation ([BMIM] + ) combined with chemically modified analogs of the bis((trifluoromethyl)sulfonyl)imide anion ([NTf 2 ] − or [TFSI] − ). The primary objective of this paper is to broaden the understanding of how the anion's conformational flexibility, fluorination, and mass affect the molecular dynamics of cations and anions. Our results indicate that flexibility has the most significant impact on the rotational and translational motions of ions. Meanwhile, the effect of fluorination and mass is only relevant when conformational flexibility does not change significantly between the ILs being compared.
Formation of highly reducible ionic liquid lead complexes in dilute aqueous solutions opens up new opportunities to employ green ionic liquids to separate heavy toxic metals efficiently.
The electrostatic interactions in ionic liquids (ILs) can be difficult to quantify, but this information is very valuable for improving intermolecular potentials for performing molecular-level simulations. Although polarizable forcefields can provide improved accuracy, the computational efficiency of fixed charge molecular models is often preferred for larger systems. Here, we propose a multi-scale screening approach for analyzing the charge scaling behavior and other electrostatic properties of ILs, which is more attainable than previous analysis methods that rely on the IL crystalline structures. Based on isolated molecules and small clusters, we study the electrostatic potential properties and charges of multivalent IL molecules using density-functional theory calculations and ab initio molecular dynamics simulations. The charges of the IL molecules are calculated and compared using several different charge estimation techniques. Although there are some differences among the estimated partial charges on the atoms, the total anion and cation charges are very similar. In conclusion, the charge scaling factors are substantial, and they are only slightly affected by the IL cluster size model.
Ionic liquids (ILs) are promising solvents for the pretreatment of lignocellulosic biomass due to their ability to disrupt cellulose, hemicellulose, and lignin structures. However, large-scale implementation requires the development of efficient recovery and recycling methods. This review provides a comprehensive analysis of the recyclability potential of ILs used in biomass pretreatment, emphasizing their mechanisms, recent innovations, and ongoing challenges. We begin by discussing the structural diversity and tunability of ILs, which underlie their effectiveness in biomass deconstruction. The distinct roles of IL anions and cations in dissolving specific biomass components are systematically presented and compared. Advances in IL recycling techniques, including antisolvent precipitation methods, membrane separation, and distillation, are critically examined, with attention to how mechanistic insights can inform the design of more efficient and selective recovery strategies. Despite progress, significant challenges remain to scaling up IL-based biomass processing, including high cost, environmental concerns, and impact of biomass-derived impurities (e.g., lignin residues, sugars, proteins) on IL purity and functionality after reuse. We also review the applicability of different ILs based on life cycle assessments and techno-economic analyses. Lastly, we identify critical research gaps and propose future directions, including the design and development of next-generation ILs with improved recyclability, reduced toxicity, and enhanced economic viability for industrial-scale applications.
The ability of functionalized ionic liquids (ILs) to provide an environment of increased stability for biomolecules has been studied. Serum albumin is an inexpensive, widely available protein that contributes to the overall colloid osmotic blood pressure within the vascular system. Albumin is used in the present study as a marker of biomolecular stability in the presence of various ILs in a range of concentrations. The incorporation of hydroxyl functionality into the methylimidazolium-based cation leads to increased protein stability detected by fluorescence spectroscopy and circular dichroic (CD) spectrometry.
As research continues for missions beyond low-Earth orbit, in-situ resource utilization (ISRU) methods are critical. For Lunar and Martian colonization, the ability to manufacture mechanical and structural components with local resources is essential. Ionic liquids (IL) are being studied at NASA Marshall Space Flight Center (MSFC) to harvest elemental metals from meteorites and regolith oxides. In this investigation, the viability of casting ductile iron using ionic liquids sourced iron and nickel was explored given ductile iron’s range of applications and performance as an as-cast alloy. Ingots were produced using commercial elements to simulate the use of IL iron with carbon sourced from the by-products of a life support system currently tested at MSFC. Samples were cast and compared to commercial ductile iron with phase transformation diagrams,microstructures, and hardness. Results showed ionic liquids sourced elements are a viable source of elemental alloying materials for a range of ductile iron alloys.