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Methods of converting lignocellulosic derivatives form 5-hydroxymethyl furfural (HMF) in ionic liquids are provided herein. Glucose is enzymatically converted to fructose by isomerization with glucose isomerase and a borate salt. Conversion of fructose to HMF includes dehydration of fructose using ionic liquids or ionic liquids with an acid catalyst to achieve high yield of HMF.
In order to explore the effect of multiple ether functionalities on ionic liquid properties, a series of ten pyrrolidinium ionic liquids and ten imidazolium ionic liquids bearing ether and alkyl side chains of varying lengths (4 to 10 atoms in length) were prepared for this study. Their physical properties, such as viscosity, conductivity and thermal profile were measured and compared. Consistent with earlier literature, a single ether substituent substantially decreases the viscosity of pyrrolidinium and imidazolium ILs compared to their alkyl congeners. Remarkably, as the number of ether units in the pyrrolidinium ILs increases there is hardly any increase in the viscosity, in contrast to alkylpyrrolidinium ILs where the viscosity increases steadily with chain length. Viscosities of imidazolium ether ILs increase with chain length but always remain well below their alkyl congeners. These results provide significant insight on the choice of starting materials for researchers designing ILs for specific applications.
Membrane-based Liquid Desiccant Air Dehumidifier (MLDAD) has the potential to overcome the shortcomings of the conventional open-tower liquid desiccant air dehumidifier. The MLDAD uses membranes with high water vapor permeability to separate air stream from the liquid desiccant and thus eliminates carry-over and the resulting corrosion issues. Recently, the ionic liquid desiccant becomes a promising alternative to conventional liquid desiccant. The ionic liquid desiccant has a large potential of dehumidification, which is also non-corrosive to metals and non-crystallizable. A two-dimensional numerical heat and mass transfer model of the MLDAD using a recently identified ionic liquid desiccant, [EMIM]OAc, is presented in this paper. We report this model can simulate the performance of the MLDAD with various designs, including different selections of liquid desiccant and membrane materials, dimensions of the MLDAD, and flow patterns. For porous membranes, this model accounts for several micro-scale mass transfer mechanisms of vapor transportation across the membrane. It can also model the mass transfer performance of dehumidifiers using non-porous membranes based on the experimentally measured membrane permeance. The numerical model was validated against the performance data available from literature and experimental tests. The maximum discrepancy of the latent effectiveness between the measured and the model-predicted results was about 6% when porous membranes were used. A parametric study was conducted with the numerical model. The results indicated that the membrane permeability, air path height, and solution to air mass ratio were the most critical parameters, determining the dehumidification performance of the MLDAD.
Membrane-based Liquid Desiccant Air Dehumidifier (MLDAD) has the potential to overcome the shortcomings of the conventional open-tower liquid desiccant air dehumidifier. The MLDAD uses membranes with high water vapor permeability to separate air stream from the liquid desiccant and thus eliminates carry-over and the resulting corrosion issues. Recently, the ionic liquid desiccant becomes a promising alternative to conventional liquid desiccant. The ionic liquid desiccant has a large potential of dehumidification, which is also non-corrosive to metals and non-crystallizable. A two-dimensional numerical heat and mass transfer model of the MLDAD using a recently identified ionic liquid desiccant, [EMIM]OAc, is presented here. This model can simulate the performance of the MLDAD with various designs, including different selections of liquid desiccant and membrane materials, dimensions of the MLDAD, and flow patterns. For porous membranes, this model accounts for several micro-scale mass transfer mechanisms of vapor transportation across the membrane. It can also model the mass transfer performance of dehumidifiers using non-porous membranes based on the experimentally measured membrane permeance. The numerical model was validated against the performance data available from literature and experimental tests. The maximum discrepancy of the latent effectiveness between the measured and the model-predicted results was about 6% when porous membranes were used. A parametric study was conducted with the numerical model. Finally, the results indicated that the membrane permeability, air path height, and solution to air mass ratio were the most critical parameters, determining the dehumidification performance of the MLDAD.
The present invention provides for novel protic ionic liquids (PIL) or phosphate-based ionic liquid (PBIL) useful for lignocellulosic processing described herein. The novel protic ionic liquids are capable of pretreatment of lignocellulosic biomass over a wide range of pH.
Abstract Ionene – ionic liquid (IL) composites are promising materials for CO 2 separation, yet a molecular‐level understanding of their structure and its impact on CO 2 speciation, solubility, rotation, and diffusivity remains unclear. Herein, using multimodal nuclear magnetic resonance (NMR), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM), and molecular dynamics (MD) simulations, we reveal that the composites contain IL‐rich domains extending across hundreds of nanometres within the ionene matrix, and these bicontinuous domains span the entire membrane depth. CO 2 also absorbs into the ionene matrix, with the distribution between two CO 2 species varying with temperature and time. The rotational correlation times of these two species are on the timescale of 0.1 and 1 ns, respectively. As IL content increases, the ionic domains expand, resulting in higher CO 2 solubility due to enhanced molecular dynamics and increased free volume in both ionene backbones and IL‐rich regions. Although CO 2 diffusion in the membranes is an order of magnitude slower than in bulk IL, the activation energy for CO 2 diffusion remains comparable. Ionene‐IL composites represent a promising platform for designing CO 2 separation membranes, offering enhanced CO 2 diffusion and selectivity through IL‐rich domains, and increased CO 2 solubility and mechanical integrity from the ionene matrix.
Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries, supercapacitors, and hybrid energy storage devices. Though Li-salt is often present in these systems, its influence on interfacial properties is largely uncharacterized. We, thereby, present an extensive computational analysis, supported by experimental comparisons, of the properties of a representative set of these electrolytesat an ideal carbon interface as a function of Li-salt doping and voltage. We have performed polarizable molecular (MD) dynamics simulations, using the APPLEP force field, to evaluate electric double layer (EDL) capacitance and distribution of Li+ in the EDL. Differential capacitance exhibits the characteristic camel profile and is insensitive to Li-doping. Li+ localizes in the second molecular layer of the EDL, which is a result of confinement from free energy barriers associated with ion layering. Joint MDelectronic structure computations show the electrochemical window of the electrolytes to be a weak function of Li-doping. Estimates of supercapacitor specific energy are made using the computed window and capacitance. The magnitude and trends in specific energy are in good agreement with experiment.
Ionic liquids (ILs) have emerged as important solvents for conversion of lignocellulosic feedstocks to fuels and chemicals due to their ability to enable efficient biomass deconstruction and fractionation. Woody biomass derived from forest and agricultural residues has the potential to be used for production of biofuels and its removal from forests can help mitigate disastrous wildfires in fire-prone states like California. This study evaluated woody biomass types (pine, almond, walnut, and fir) from California as potential biofuel feedstocks. The feedstocks were pretreated with the ILs cholinium lysinate ([Ch][Lys]) and ethanolamine acetate ([EOA][OAc]), followed by enzymatic hydrolysis and fermentation of lignocellulosic sugars to produce ethanol. Under optimal conditions, [EOA][OAc] pretreatment and enzymatic hydrolysis generated glucose and xylose yields in the range of 24-82 and 14-80%, respectively, while glucose and xylose yields for the [Ch][Lys] ranged between 28-83 and 23-80%, respectively. Maximum fermentable sugar was released from almond wood, and the lowest amount was from pine and fir. Further, blends of feedstocks were also explored, and a blend with a mass ratio of 2/2/1 (almond/walnut/pine) resulted in maximum glucose and xylose (>90%) yields using [Ch][Lys]. Fermentation of this hydrolysate using a C5-utilizing strain of Saccharomyces cerevisiae resulted in a maximum ethanol concentration of 17.9 g/L for mixture biomass hydrolysate, corresponding to 60.8% fermentation efficiency. This study represents the first demonstration of the use of these ILs for pretreatment of woody biomass blends that resulted in a high overall conversion efficiency for ethanol production.
The formation of an electric double layer in ionic liquid (IL) can electrostatically induce charge carriers and/or intercalate ions in and out of the lattice which can trigger a large change of the electronic, optical, and magnetic properties of materials and even modify the crystal structure. Here, we present a systematic study of ionic liquid gating of exfoliated 2D molybdenum trioxide (MoO 3 ) devices and correlate the resultant electrical properties to the electrochemical doping via ion migration during the IL biasing process. A nearly 9 orders of magnitude modulation of the MoO 3 conductivity is obtained for the two types of ionic liquids that are investigated. In addition, notably rapid on/off switching was realized through a lithium-containing ionic liquid whereas much slower modulation was induced via oxygen extraction/intercalation. Time of flight–secondary ion mass spectrometry confirms the Li intercalation. Density functional theory (DFT) calculations have been carried out to examine the underlying metallization mechanism. Results of short-pulse tests show the potential of these MoO 3 devices as neuromorphic computing elements due to their synaptic plasticity.
The ionic-liquid/graphite interface is important in understanding the behaviors of the ionic-liquid electrolyte in carbon-based supercapacitors and Li-ion batteries. A row-like cation–anion structure of the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP][TFSA]) ionic liquid (a popular choice for interfacial studies) on the graphite surface has been suggested on the basis of scanning tunneling microscopy images, but it is unclear if this structure is the most stable one. Herein, we explore alternative models of the [BMP][TFSA] monolayer on graphite basal plane with first-principles density functional theory. We find that the checkerboard type of structure is in fact more stable than the row-like structure. We further use simulated annealing based on classical molecular dynamics simulations to obtain more stable conformations of ions on the surface. Both charge-density-difference and noncovalent-interaction analyses show that the higher stability of the checkerboard structure than the row-like structure is due to the stronger anion–surface interactions in the former. Furthermore, our work therefore suggests a new structure of the [BMP][TFSA] monolayer on the graphite basal plane.
An ionic liquid that is a salt has a Formula: ##STR00001## Such ionic liquids may be used in electrolytes and in electrochemical cells.
An ionic liquid that is a salt has a Formula: ##STR00001## Such ionic liquids may be used in electrolytes and in electrochemical cells.
The current study made a comprehensive literature review of the structure activity relationship (SAR) for microcidal and virucidal influence of ionic liquids. It summarized the key structure parameters that have close correlation to the antimicrobial and antiviral properties of the ILs. It proposed an experimental plan on developing and testing an effective ionic liquid from renewable lignocellulosic biomass. The goal is to understand the structure activity relationship (SAR) for virucidal influence of ionic liquids through comprehensive literature search and data analysis. A full experimental plan will be drafted based on the literature summary. Perform a comprehensive literature search to aid the development of an effective and easily deployable method to inactivate SARS-CoV-2 and decontaminate surfaces based on low-cost functional ionic liquids. These designer solvents have the potential to be a compelling and environmentally friendly alternative to common chemical disinfectants. Literature summary report including reported ionic liquid structures, synthesis and testing methods, and the structure activity relationship. Experimental plan on developing a low cost effective antiviral ionic liquid.
We report an in situ measurement of the interaction of an imidazolium-based room temperature ionic liquid with both pure silver and a graphene-over-silver electrode under an applied electrochemical potential. At a negative applied potential, overall signal intensity increased indicating enhanced ionic liquid concentration at both silver and graphene electrodes. Vibrational modes associated with the imidazolium ring exhibited greater intensity enhancements and larger peak shifts compared with the anion indicating that the cation adsorbs with the ring and alkyl chain parallel to the electrode surface for both silver and graphene. In contrast to the silver, the surface enhanced Raman spectra of the ionic liquid near graphene showed shifts in the cation peaks even at no applied potential because of the strong π–π interaction between the ionic liquid and the graphene. Furthermore, the intensity of the graphene peak decreased in the presence of ionic liquid possibly due to the interaction between the ionic liquid and graphene. In conclusion, these results illustrate the effectiveness of surface-enhanced Raman spectroscopy to investigate electrolyte interactions with graphene at the liquid/electrode interface.
Fluorine-containing anions are widely used in ionic liquids due to their unique physicochemical properties. However, the local dynamics of both cations and anions and their associated relaxation mechanisms remain incompletely understood. Here, we present a 1 H and 19 F spin–lattice relaxation rate (R1) study as a function of frequency over a broad frequency range from 30 kHz to 800 MHz for ionic liquids containing BF 4 – , PF 6 – , TFSI – , and FSI – anions and EMIM + cation. By combining experimental R 1 H and R 1 F NMR dispersion (NMRD) profiles with relaxation models for both dipolar spin interactions and chemical shift anisotropy (CSA) contributions, we demonstrate that CSA is needed to accurately describe the R 1 F relaxation behavior above ∼300 MHz, the extent of which depends on the anion structure. These findings challenge the long-standing assumption that dipolar contribution is the main source of 19 F relaxation in these systems and highlight the importance of including CSA to accurately interpret 19 F relaxation in ionic liquids, particularly at high frequencies. This work provides new insights into the molecular dynamics of fluorine-containing species.
Solvent extraction of La 3+ and Ba 2+ by an ionic liquid extractant in an imidazolium-based ionic liquid diluent was investigated. Seven protic ionic liquid extractants were examined and these protic ILs are based on five organic superbases and either 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione (Hfod) or 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) -diketones as anion. For fod-based extractants, the extraction efficiencies and separation factors were found to be concentration dependent. The effects of aqueous phase acidity, extractant structure, and extractant concentration on separation properties of La 3+ and Ba 2+ are discussed in this paper.
In this paper, five new room temperature ionic liquids were tested as supported ionic liquid membranes (SILMs) for CO 2 /N 2 separation capability. This series of ionic liquids (ILs) contains bicyclic amidine cations of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with small alkyl chain substituents. These ILs have been synthesized to examine the effects of cation structure on free volume. Relevant physical and chemical properties have been examined, including CO 2 solubility and viscosity. The relationship between fractional free volume and permeability of gases is explored, with an interesting note on solubility. Each cation was paired with two different anions: bis(trifluoromethanesulfonyl)imide and tetracyanoborate, for further investigation of the cation-anion interaction on SILM permeability and selectivity. Finally, three of these new ILs have exceeded Robeson's upper bound for CO 2 /N 2 gas separations.
The viscosity of mixtures of pyrrolidinium-based ionic liquids saturated with compressed CO 2 was measured using a high-pressure viscometer at three different temperatures (298.15, 318.15 and 338.15 K). The high-pressure viscosity of 1-propyl-1-methyl-pyrrolidinium ([C 3 C 1 pyr]), 1-butyl-1-methyl-pyrrolidinium ([C 4 C 1 pyr]), and 1-hexyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide ([C 6 C 1 pyr]) cations with common anion, bis(trifluoromethylsulfonyl)amide ([NTf 2 ]), was measured up to a maximum CO 2 pressure of 25 MPa. In the temperature range investigated, the viscosity of the ionic liquid/ CO 2 mixture dramatically decreases with increasing of CO 2 pressure up to approximately 7 MPa but the viscosity decrease becomes less significant at higher CO 2 pressures (from 7 to 25 MPa) because the CO 2 composition in ILs slightly increases with pressure. At lower CO 2 pressures (compositions), temperature has a higher impact on the CO 2 solubility in IL, thus the viscosity drops significantly for lower temperatures (e.g. 298.15 K). The effect of alkyl chain length of the cation on the viscosity of ionic liquid/ CO 2 mixture was also measured. Though the pure [C n C 1 pyr][NTf 2 ] viscosity increases significantly with the increasing alkyl chain length of the cation, the viscosity of every ionic liquid/ CO 2 mixture tested herein become quite similar at higher CO 2 pressures, for a fixed temperature.