Ionic Liquid Research Articles

Descriptors for Electrochemical CO2 Reduction in Imidazolium-Based Electrolytes.

Electrochemical CO2 reduction (CO2R) allows us to close the carbon cycle and store intermittent renewable energy into chemical products. Among these, syngas, a mixture of hydrogen and carbon monoxide, is particularly valuable due to its high market share and the low energy required for its electrocatalytic production. In addition to catalyst optimization, lately, electrolyte modifications to achieve a suitable CO/H2 ratio have also been considered. Ionic liquid (IL)-based electrolytes have enabled high faradaic efficiency toward CO, depending on the chemical properties of the IL. In this work, we rationalized through density functional theory (DFT) descriptors the competition between hydrogen evolution (HER) and CO2R on silver in imidazolium-based electrolytes, developing a DFT-based analytical model. The electrolyte anion regulates the concentration ratio between cationic and carbene species of ILs cation, respectively, between the 1-ethyl-3-methylimidazolium cation (EMIM+) and carbene (EMIM:) species and between the 1-butyl-3-methylimidazolium cation (BMIM+) and carbene (BMIM:). The latter species, if formed, hinders the CO2R by blocking the active sites or trapping CO2 in solution. In the case of weak Lewis base anions as fluorinated ones, EMIM+ (BMIM+) cations, which serve as cocatalysts in CO2R, are more abundant, allowing high CO partial current densities and high electrochemically active surface area. Applying the here-defined descriptors to ILs not yet tested makes it possible to predict the HER and CO2R selectivity on silver, thus enabling guidelines for designing better ILs for CO2R.

Translational Dynamics of Cations and Anions in Ionic Liquids from NMR Field Cycling Relaxometry: Highlighting the Importance of Heteronuclear Contributions.

NMR field cycling relaxometry is a powerful method for determining the rotational and translational dynamics of ions, molecules, and dissolved particles. This is in particular true for ionic liquids (ILs) in which both ions carry NMR sensitive nuclei. In the IL triethylammonium bis(trifluoromethanesulfonyl)imide ([TEA][NTf2]), there are 1H nuclei at the [TEA]+ cations and 19F nuclei at the [NTf2]- anions. Moreover, the high viscosity of this IL leads to frequency-dependent relaxation rates, leaving the so-called extreme narrowing regime. Both the rotational and the translational dynamics of the constituents of ILs can be obtained by separating the contributions of intra- and intermolecular relaxation rates. In particular, the translational dynamics can be obtained separately by applying the so-called "low-frequency approach" (LFA), utilizing the fact that the change in the total relaxation rates at low frequencies results solely from translational motions. However, for systems containing multiple NMR active nuclei, heteronuclear interactions can also affect their relaxation rates. For [TEA][NTf2], the intermolecular relaxation rate is either the sum of 1H-1H cation-cation and 1H-19F cation-anion interactions or the sum of 19F-19F anion-anion and 19F-1H anion-cation interactions. Due to the lack of available experimental information, the 1H-19F heteronuclear intermolecular contribution has often been neglected in the past, assuming it to be negligible. Employing a suitable set of ILs and by making use of isotopic H/D substitution, we show that the 1H-19F heteronuclear intermolecular contribution in fact cannot be neglected and that the LFA cannot be applied to the total 1H and total 19F relaxation rates.

High-Energy LiNiO2 Li Metal Batteries Enabled by Hybrid Electrolyte Consisting of Ionic Liquid and Weakly Solvating Fluorinated Ether.

In pursuit of the highest possible energy density, researchers shift their focus to the ultimate anode material, lithium metal (Li0), and high-capacity cathode materials with high nickel content (Ni > 80%). The combination of these aggressive electrodes presents unprecedented challenges to the electrolyte. Here, wereport a hybrid electrolyte consisting of a highly fluorinated ionic liquid and a weakly solvating fluorinated ether, whose hybridization structure enables the reversible operation of a battery chemistry based on Li0 and LiNiO2 (Ni = 100%), delivering nearly theoretical capacity of the latter (up to 249mAhg-1) for >300cycles with retention of 78.6% and in absence of unwanted morphological changes in both electrodes. Extensive characterization assisted by molecular dynamic simulation and density functional theory calculations reveals the function of the fluorinated ether to be far more profound than simple dilution and viscosity reduction. Instead, it induces drastic changes in Li+-solvation environment, the consequence of which engenders simultaneous stabilization of electrode/electrolyte and interfacing via formation of respective interfacial chemistries. This study further unlocks fundamental knowledge underneath the prevailing "diluent strategy" that is extensively applied by the electrolyte researchers and opens more design space for the next-generation electrolytes and interphases for these coveted battery chemistries.

Development of thermomorphic ionic liquids derived from organophosphorus acids for homogeneous extraction processes

Development of thermomorphic ionic liquids derived from organophosphorus acids for homogeneous extraction processes

Closing the Loop: Recyclable Solvate Ionic Liquids in Solid Polymer Electrolytes for Circular Economy

Closing the Loop: Recyclable Solvate Ionic Liquids in Solid Polymer Electrolytes for Circular Economy

Second law of thermodynamics, heat transfer, and pumping power analyses of water and ionic liquid mixture based MXene nanofluids in a shell and helical coil heat exchanger

Heat exchangers are extensively employed across diverse sectors for efficient thermal (heat)transfer between two fluids, specifically from a hot fluid to a cold fluid. Nanofluids are promising heat transfer fluids that exhibit exceptional thermal performance in heat exchangers. The present study examines the thermodynamic second law efficiency analysis of a shell and helical coil heat exchanger utilizing MXene/80:20% water+[MMIM][DMP] (mass percentage) based ionanofluids. An analytical investigation was conducted on the heat transfer coefficient, entropy generation rate, and exergy efficiency of a shell and helical coil heat exchanger, considering particle weight loadings from 0.2% to 1.0%, Reynolds numbers from 500 to 4300, and flow rates from 0.5 to 3.5 L/min. In the base fluid, at 1.0 wt.% and at a Reynolds number of 3598, the increase in heat transfer, Nusselt number, friction factor, pressure drop, effectiveness, and frictional entropy generation are 45.59%, 28.27%, 15.19%, 12.56%, 17.20%, and 16.21%, respectively. Concurrently, thermal entropy generation, and total exergy destruction were reduced by 46.23% and 20.08%, respectively. The second law (exergy) efficiency and thermal performance factor are improved by 34.04% and 1.384-times, respectively, at 1.0 wt.% and at a Reynolds number of 3598, compared to the base fluid. The data from the current study is corroborated by existing literature. New correlations were developed from the computed data points to estimate the Nusselt number and friction factor.

Boosted electrochemical reduction detoxification and oxidation of clofibric acid by polymerized ionic liquid functionalized cathode: Parameter optimization and degradation mechanisms

The application of electrocatalytic degradation technology in the treatment of pharmaceuticals and personal care products (PPCPs) has attracted widespread attention currently. Through structure and properties characterization of catalysts we found that more uniformly distributed metal particles and excellent thermal stability were obtained by modification with poly(1-vinyl-3-butylimidazole hexafluorophosphate) ([(PV)BIM]PF6) on graphene to anchor the metal CoNi nanoparticles (CoNi/PILs-rGO). For assessing its application potential, the CoNi/PILs-rGO cathode in combination with Ti/RuO2/IrO2 anode to set up an experimental reaction system for the electrocatalytic degradation of clofibric acid (CA) simulated wastewater. Reactor settings for experimentation are optimized, and intermediates, alterations in toxicity during degradation, and active species are detected. The results of the single-factor experiment showed that the average removal rate of CA by the cathodic compartment was 97.18 % when the conditions were optimal. Two possible pathways of degradation are deduced from the CA intermediates, one is the C-Cl bond breaking in electrochemical reduction, and the other is that the C-O bond is directly broken by anodic reactive oxygen. Toxicity tests have shown that the anode produces some by-products that are more hazardous than the original chemical, while the cathode produces a dechlorination process that is ultimately more detoxifying.

Exploring the impact of Anions, Alkyl group and confinement effect in ionic liquid @ UiO-66(Zr) MOF: A DFT study

Metal organic frameworks (MOFs) have emerged as a strong research material due to their exceptional porosity and tunable functional nature. MOF structures consist of metal nodes with organic linker, which can be functionalized depending on the required application. With the tunable properties, it has wide range of applications in energy, environmental and therapeutic approaches. Nevertheless there are several factors which can affect their performance such as lower affinity towards target molecules, chemical and thermal stability etc. To counter these issues several studies have been devoted on functionalizing the MOF. In this work, we have considered UiO-66 (University of Oslo-66) MOF because of its exceptional thermal and chemical stability with a series of versatile ionic liquids (ILs). The selected ILs are 1-ethyl-3-methylimidazolium ([C2MIm]+) and 1‑butyl‑3-methylimidazolium ([C4MIm]+) cations with various anions [X]−, where X = acetate (OAc), tetrafluroborate (BF4), dicyanamide (DCA), nitrite (NO2) and chloride (Cl) anions. These ILs have been impregnated in tetrahedral (∼10 Å) and octahedral (∼16 Å) pores of UiO-66 structure. First principle density functional theory (DFT) approach is used to study the structure, stability, spectral properties and charge transfer between IL/UiO-66 interfaces. Our calculations suggest that, IL does not affect the structure of UiO-66 surface. The anion and the alkyl group in the cations play a vital role in the stability of the complexes. Furthermore, confinement effect influence the stability of the complexes, irrespective nature of anion and cation. Electron density and charge transfer analyses reveal that anions have profound liking towards MOF because of having high electronegative atoms. Our study will help to understand the molecular level interaction between IL@MOF interface, and these composite can be utilized for the energy and environment related applications.

Development of an ionic liquid-based microextraction system (ILBME) for sensitive spectrophotometric analysis of neodymium(III) ions in environmental samples

ABSTRACT Introducing a precise, sensitive and simple system for determining neodymium(III) ions in aquatic samples could enhance the capabilities of routine instruments, particularly in terms of detection limits. Coupling a powerful preconcentration system, such as ionic liquid-based microextraction (ILBME), with a spectrophotometer can successfully achieve this goal. A sensitive and simple microextraction method based on a task-specific ionic liquid, designated [PDmim][Cl2], is described, in which the imidazolium-based ionic liquid served dual roles as both the chelating agent and the extraction phase. The ionic liquid was synthesized and characterized before being applied in microextraction procedure. The optimized microextraction results indicate that neodymium concentrations up to 5.10 µg L−1 can be successfully determined. The method characteristics, including the limit of detection (LOD), limit of quantification (LOQ), intra-day and inter-day relative standard deviations (RSDs), preconcentration factor (PF), enrichment factor (EF) and linear dynamic range (LDR), were found to be 1.53 µg L−1, 5.10 µg L−1, 3.83%, 4.44%, 123, 111.1 and 5.0–125.0 µg L−1, respectively. For method validation, the standard addition method using standard reference material (SRM) was employed, and the recovery range from real samples analyses was between 99.3% and 101.0%.

Multiphase Coexistence in an Ionic Liquid: 1-Decyl-3-methylimidazolium Nitrate.

Complicated phase transitions were observed in a single-component 1-decyl-3-methylimidazolium nitrate ([C10mim][NO3]) ionic liquid (IL) using Raman spectroscopy and synchrotron small- and wide-angle X-ray scattering (SWAXS). Time-resolved synchrotron SWAXS could distinguish the phase transitions depending upon the cooling rate. Low-Q peaks representing a few kinds of layered structures were decomposed. Multiphase coexistence was observed in [C10mim][NO3] at specific cooling rates (8-9 K/min). Ionic liquid crystals (ILCs), hybrid-layered crystals, and hexagonal close-packed structures coexisted simultaneously. At the cooling rate region, the reentrant phase transition of the ILC phase upon heating was observed.

Mechanism of selectivity of tri-n-octylmethylammonium chloride for vanadium

Ionic liquid (IL)-based extraction is a promising and environmentally benign separation technology. Processes for quaternary ammonium-based IL extraction of vanadium have been extensively studied, but the vanadium extraction mechanism has not been accurately confirmed. This study investigated vanadium extraction from sulphuric acid leachate of shale by solvent extraction with tri-n-octylmethylammonium chloride (TOMAC/CH3NClR3). The results indicated that 90.50 % of the vanadium extraction percentage comprised one stage under the optimal condition experiments. These experiments were carried out at pH 1.8; the IL phase consisted of 25 vol% TOMAC, 15 vol% TBP, and 60 vol% sulfonated kerosene; O/A phase ratio of 1:7.5; extraction time of 120 s. The forms of vanadium and impurities present were revealed by the solution chemistry, Medusa software simulation. The extraction mechanism of vanadium was investigated using ultraviolet spec-trophotometer (UV–Vis), fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), and hotometer matrix-assisted laser-resolved ionization time-of-flight mass spectra (MALDI-TOF-MS). Under extraction conditions at pH 1.8, vanadium was present as an anion in the form H2V10O4- 28 and HV10O5- 28. Since the extraction mechanism of TOMAC was anion exchange, the extracted vanadium was mainly present as the anionic complex [(CH3NR3)4·H2V10O4- 28]/[(CH3NR3)5·HV10O5- 28]. The ESP map of TOMAC and V (V) was calculated to confirm the reaction sites and was used to verify the anion exchange mechanism.

Mechanistic insights on stabilization and destabilization effect of ionic liquids on type I collagen fibrils

Tuned assembly of collagen has tremendous applications in the field of biomedical and tissue engineering owing to its targeted biological functionalities. In this study, ionic liquids choline dihydrogen citrate (CDHC) and diethyl methyl ammonium methane sulfonate (AMS) have been used to regulate the self-assembly of collagen at its physiological pH by probing the assembled systems at certain concentration ratios of ionic liquids and the systems were studied using various characterization methods. Due to interaction with collagen, choline dihydrogen citrate causes delay in the collagen fibrillisation process showing no binding interactions with collagen. In contrast, diethyl methyl ammonium methane sulfonate shows crosslinking effect on collagen fibrillisation due to the electrostatic interaction with the tetrahedral hydration shell of collagen moieties. From rheological studies it was observed that the AMS treated collagen fibril at 1:1 % (w/v) has highest linear viscoelastic range, this can bear the stress under high strain compare to native collagen fibril as well as all CDHC composites. For a sustainable biomaterial or bio-scaffold, mechanical property plays pivotal role on it and from our experimental analysis we found certain composites of ionic liquid treated collagen fibrillar assembly which may act as a sustainable biomaterial or bio-scaffold. It was also evolved that, how the structure-function relationship of ionic force modulated fibrillar assembly controlling the mechanical properties of the tuned system. This self-assembled, ionic-liquid treated collagen-fibrillar system would accelerate various force modulated fibrillar network study, for mimicking the ECM and tissue engineering application.

Polymerizable Ionic Liquid-Derived N, S co-Doped sp3/sp2 Carbon as Electrocatalyst for H2O2 Generation.

The H2O2 generation via the green electrochemical process is of high interest. For the H2O2 electrochemical generation, the oxygen reduction reaction (ORR) is important. Unfortunately, the ORR is kinetically sluggish and catalysts are needed. However, noble metal ORR catalysts are pricy and scarcely applicable in applications. Therefore, non-precious metal catalysts are desired. Heteroatom-doped carbons show promise as metal-free ORR catalysts. The ORR catalytic activity will be enhanced by the carbon's sp2 and/or sp3 engineering. For N, S co-Cdoped and sp2/sp3 modulated carbon, a polymerizable ionic liquid of hydrolyzed vinyl imidazolium was studied. The carbon is studied as a metal-free catalyst for the ORR via the 2e- process. It is possible to get an onset potential of 0.88 V vs. RHE with approximately 50 % selectivity for the H2O2. The current study offers a simple technique for synthesizing heteroatom-doped sp2/sp3 designed carbon as catalysts for the electroreduction of O2 to produce H2O2, and a new way of tunning the sp3/sp2 carbon catalytic activity by modulating the ionic liquid.

Molecular dynamics simulations of uranyl and plutonyl cations in a task-specific ionic liquid.

Ionic liquids (ILs) are a unique class of solvents with potential applications in advanced separation technologies relevant to the nuclear industry. ILs are salts with low melting points and a wide range of tunable physical properties, such as viscosity, hydrophobiciy, conductivity, and liquidus range. ILs have negligible vapor pressure, are often non-flammable, and can have high thermal stability and a wide electrochemical window, making them attractive for use in separations processes relevant to the nuclear industry. Metal salts generally have a low solubility in ILs; however, by incorporating new functional groups into the IL cation or anion that promote complexation with the metal, the solubility can be greatly increased. One such task-specific ionic liquid (TSIL) is 1-carboxy-N, N, N-trimethylglycine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) [Nockemann et al., J. Phys. Chem. B 110, 20978-20992 (2006)]. Water, which is detrimental for electrochemical separations, is a common impurity in ILs and can coordinate with actinyl cations, particularly in ILs containing only weakly coordinating components. Understanding the behavior of actinides in TSIL/water mixtures on a molecular level is vital for designing improved separations processes. Classical molecular dynamics simulations of uranyl(VI) and plutonyl(VI) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf2N]) with deprotonated Hbet (betaine) and water have been performed to understand the coordination and dynamics of the actinyl cations. We find that betaine is a much stronger ligand than water and prefers to coordinate the metal in a bidentate manner. Potential of mean force simulations yield a relative free energy for betaine coordination of approximately -120 to -90 kJ/mol in mixtures with water. As the amount of betaine coordinated to the actinide increases, the diffusion coefficient of the actinyl cation decreases. Moreover, the betaine ligand is able to bridge between two metal centers, resulting in dimeric complexes with actinide-actinide distances of ∼5Å. Potential of mean force simulations show that these structures are stable, with relative free energies of up to -40 kJ/mol. The crystal structure for [(UO2)2(bet)6(H2O)2][Tf2N]4 shows that the betaine bridges between two uranium atoms to form dimeric complexes similar to those found in our simulations [Nockemann et al. Inorg. Chem. 49, 3351-33601 (2010)].

Investigating the Role of Anions in the Adsorption of Pyrrolidinium Based Ionic Liquids on Pt(111) Surface Using Density Functional Theory

ABSTRACTThe adsorption properties of ionic liquids containing pyrrolidinium cations and various inorganic anions as electrolytes on a platinum surface were analyzed using first principle density functional theory. Three different orientations of the alkyl cation chain were observed during the adsorption process. The strength and structural stability varied between non‐fluorinated and fluorinated anions upon adsorption, with oxygen atoms influencing the mechanism of adsorption and driving the structural stability of the anion, while fluorine atoms played a role in determining the orientation of the cation during adsorption. Net atomic charges analysis, electron density difference methods, and electron density accumulation for this complex system were utilized to further investigate these phenomena. The results of this study provide valuable insights into the role of anions in the adsorption behavior of pyrrolidinium‐based ionic liquids on platinum surfaces, shedding light on the factors that influence their adsorption properties and structural stability on a molecular level. The findings of this study contribute to a better understanding of the interplay between anions and platinum surfaces in the adsorption of pyrrolidinium based ionic liquids, which can have implications for various applications such as electrochemistry, catalysis, and energy storage.

Enhancing performance and sustainability of lithium manganese oxide cathodes with a poly(ionic liquid) binder and ionic liquid electrolyte

Current battery production involves various energy intensive processes and the use of volatile, flammable and/or toxic chemicals. This study explores the potential for using a water-soluble and functional binder, poly(diallyldimethylammonium) (PDADMA) with diethyl phosphate (DEP) as a counter anion, for lithium manganese oxide (LMO) cathodes. By replacing the traditional polyvinylidene fluoride (PVDF) binder and its associated toxic N-methyl-2-pyrrolidone (NMP) solvent, PDADMA-DEP offers a more sustainable and cost-effective solution. Notably, PDADMA-DEP electrodes do not require high-temperature calendaring to achieve high performance unlike PVDF electrodes. X-ray Photoelectron Spectroscopy (XPS) indicated significant interactions between the binder and LMO that enhance stability and ion conduction. The PDADMA-DEP binder demonstrated excellent electrochemical rate capability up to 10C with the conventional organic liquid electrolyte (LP30), outperforming PVDF electrodes. The performance of both binders using a safer and non-volatile ionic liquid electrolyte, specifically 50 mol% LiFSI in N-trimethyl-N-propylammonium bis(fluorosulfonyl)imide, was also investigated to enhance the overall safety and environmental impact of the battery system. IL-based cells utilizing a PDADMA-DEP cathode binder demonstrated a 58 % capacity retention over 500 cycles at 0.5C when cycled at room temperature.

Experimental and theoretical studies of physicochemical properties of Gemini imidazolium ionic liquids: hydroxyl group in spacer chain and alkyl chain length of cation

Experimental and theoretical studies of physicochemical properties of Gemini imidazolium ionic liquids: hydroxyl group in spacer chain and alkyl chain length of cation

Understanding ultrafast rechargeable Al/graphite battery by visualizing phase separation

Al/graphite batteries (ABs) using ionic liquid electrolytes exhibit exceptionally fast charging and cycling stability. However, the mechanisms underlying their high rate capabilities remains elusive. In this study, in situ optical microscopy is employed to investigate the intercalation dynamics of single-flake graphite in ABs. Observations reveal that surface reaction limitations, rather than AlCl4− mass transfer, primarily govern performance in the graphite cathode. During charging under varying current densities, the ABs display distinct phase separation behaviour with an intercalation wave morphology, indicating that surface reactions restrict the intercalation process. This finding explains the ultrafast recharge capability of ABs, where active sites in graphite become nearly fully intercalated with AlCl4− at high current densities. Additionally, slight rate performance loss occurs due to increasing ohmic and charge transfer polarisation (ηohm and ηct) at higher current densities. To address this limitation, we propose increasing the cut-off voltage as a straightforward and effective method to mitigate these polarization effects. This study offers valuable insights into the electrochemical behaviour of rechargeable secondary ion batteries by visualising their phase separation.

Conversion of atmospheric CO2 catalyzed by thiolate-based ionic liquids under mild conditions: efficient synthesis of 2-oxazolidinones.

Thiolate-based ionic liquids, specifically the catalyst [TBP][2-Tp], have demonstrated their efficiency in catalyzing the reaction of CO2 with propargylic amine. This novel synthetic method can be used to synthesize various 2-oxazolidinone derivatives with high yields. The catalyst can be easily regenerated and reused without any decline in its catalytic activity. Experimental and spectroscopic investigations have confirmed that the high activity of [TBP][2-Tp] is attributed to the synergistic effect of its S and N sites in activating CO2, rather than depending solely on basicity to activate the amino group of propargylic amine. These findings highlight the significant potential of thiolate-based ionic liquids for applications in CO2 activation and conversion.

Evaluating the Hydrothermal Stability of Superbase-Based Ionic Liquids in Cellulose Fiber Spinning.

This study highlights the substantially improved hydrothermal stability of 7-methyl-1,5,7-triazabicyclo[4.4.0] dec-5-enium [mTBDH]+ in [mTBDH][MeOCH2COO] compared to [mTBDH][OAc], as well as the strong cellulose dissolution capability of [mTBDH][MeOCH2COO] and excellent spinnability with a maximum draw ratio of 14. These findings demonstrate the high potential of using [mTBDH][MeOCH2COO] as the solvent to advance Ioncell fiber spinning technology by reducing the hydrolysis rate of [mTBDH]+, thereby minimizing loss during solvent recycling processes.