Molecular simulation study of the microstructures and properties of pyridinium ionic liquid[HPy][BF_(4)]mixed with acetonitrile

The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this work.The following properties were determined:density,self-diffusion coefficient,excess molar volume,and radial distribution function.The results show that with an increase in the mole fraction of[HPy][BF_(4)],the self-diffusion coefficient decreases.Additionally,the excess molar volume initially decreases,reaches a minimum,and then increases.The rules of radial distribution functions(RDFs)of characteristic atoms are different.With increasing the mole fraction of[HPy][BF_(4)],the first peak of the RDFs of HA1-F decreases,while that of CT6-CT6 rises at first and then decreases.This indicates that the solvent molecules affect the polar and non-polar regions of[HPy][BF_(4)]differently.

Effects of ionic liquids on the vapor-liquid equilibrium of 1,3,5-trioxane-water system at 101.3 kPa

Increasing the 1,3,5-trioxane(TOX) concentration in the equilibrated vapor phase of TOX-H_(2)O system has been recognized as a challenge for the azeotrope. Ionic liquids(ILs) were used to improve the relative volatility of TOX to H_(2)O and destroy the azeotrope in the TOX-H2O system. The vapor-liquid equilibrium of TOX-H2O system at 101.3 kPa was studied with the addition of 1-butyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate and 1-butyl-3-methylimidazolium nitrate, respectively. The results showed that the volatility of TOX increased with the increase in IL dosage. And the volatility of water decreased with the increase in IL dosage. The relative volatility of TOX to H_(2)O was improved with the increase in ILs dosage. The azeotrope could be destroyed with an IL mole fraction of about 0.10. A non-random two-liquid(NRTL) model was successfully used to correlate the experimental data. The interaction parameters were obtained by fitting the experimental data with the model. The results indicated that a strong interaction existed between ILs and water. The strong interaction improved the volatility of TOX and inhibited the volatility of water, and then intensified the relative volatility of TOX to H_(2)O. The results showed that an ILs with strong polarity and hydrophilicity may be a potential additive to improve the TOX concentration in the equilibrated vapor phase.

Interfacial friction induced capillary flow within nanofiber-supported ionic liquid droplets

As global economic growth increases,the demand for energy sources boosts.While fossil fuels have traditionally satisfied this demand,their environmental influence and limited reserves require alternatives.Fossil fuel combustion contributes substantially to greenhouse gas emissions,with a pressing need to halve these emissions by 2030 and target net-zero by 2050.Renewable energy sources,contributing currently to 29%of global electricity,are viewed as promising substitutes.With wind energy's potential,Zheng's team developed a novel method to harness even low wind speeds using well-aligned nanofibers and an innovative“drop wind generator”.This system,combining moisture-saturated ionic liquid 3-Methyl-1-octylimidazolium chloride with specific nanofiber arrays,exploits wind-inducedflows for energy conversion.This study highlights the vast untapped potential of low-speed wind as a sustainable energy source potentially for electronics.

Self-separation ionic liquid catalyst for the highly effective conversion of H_(2)S by α,β-unsaturated carboxylate esters under mild conditions

The deep-processing utility of pure hydrogen sulfide (H_(2)S) is a significant direction in natural gas chemical industry.Herein,a brand-new strategy of H_(2)S conversion by a,β-unsaturated carboxylate esters into thiols or thioethers using task-specific carboxylate ionic liquids (ILs) as catalyst has been developed,firstly accomplishing the phase separation of product and catalyst without introducing the third component.It can be considered as a cascade reaction in which the product selectivity can be controlled by adjusting the molar ratio of H_(2)S to a,β-unsaturated carboxylate esters.Also,the effects of ILs with different anions and cations,intermittent feeding operations,as well as pressure-time kinetic behaviors on cascade reaction were investigated.Furthermore,the proposed interaction mechanism of H_(2)S conversion using butyl acrylate catalyzed by[Emim][Ac]was revealed by DFT-based theoretical calculation.The approach enables the self-phase separation promotion of catalyst and product and achieves 99%quantitative conversion under mild conditions in the absence of solvent,making the entire process ecologically benign.High-efficiency reaction activity can still be maintained after ten cycles of the catalyst.Therefore,the good results,combined with its simplicity of operation and the high recyclability of the catalyst,make this green method environmentally friendly and cost-effective.It is anticipated that this self-separation method mediated by task-specific ILs will provide a feasible strategy for H_(2)S utilization,which will guide its application on an industrial scale.

Highly defective HKUST-1 with excellent stability and SO_(2) uptake: The hydrophobic armor effect of functionalized ionic liquids

Water stability is one of the most important factors restricting the practical application of metal organic frameworks (MOFs). In this work, wefabricate a highly defective HKUST-1 framework with a mixed valence of CuI/CuIIby mechanical ball milling method. This defective HKUST-1is embellished by functionalized ionic liquids as hydrophobic armor, making the hybrid HIL1@HKUST-1 exhibits outstanding water stability,remarkable SO_(2) adsorption (up to 5.71 mmol g^(-1)), and record-breaking selectivity (1070 for SO_(2)/CO_(2) and 31,515 for SO_(2)/N_(2)) at 25 ℃ and0.1 bar, even in wet conditions.

固定Ionic liquid/Silica sol/Nafion膜中的联吡啶钌电化学发光行为的研究及应用

制备了Ionic liquid/Silica sol/Nafion-联吡啶钌复合物膜修饰金电极。采用循环伏安(CV)和电致化学发光(ECL)法,考察了联吡啶钌和左氧氟沙星在此修饰电极上的电化学及其发光行为。结果表明,此修饰电极表现出很好的电化学活性和电化学发光响应。基于左氧氟沙星对固定化联吡啶钌在0.1 mol/L磷酸盐缓冲液中的弱电化学发光信号有较强的增敏作用,建立了电化学发光检测盐酸左氧氟沙星的新方法。在最佳实验条件下,左氧氟沙星浓度在1.0×10-7～1.0×10-4mol/L范围内与相对发光强度呈线性关系(r2=0.998 4),检出限(S/N=3)为1.59×10-9mol/L。连续平行测定2.2×10-5mol/L的左氧氟沙星溶液10次,发光强度的相对标准偏差(RSD)为3.6%。对样品进行回收率试验,回收率在95.6%～103.5%之间,RSD(n=5)为3.0%。该方法具有较高的选择性和灵敏度,样品处理简单快速,用于盐酸左氧氟沙星的测定,结果满意。

An ionic liquid-assisted strategy for enhanced anticorrosion of low-energy PEO coatings on magnesium–lithium alloy

A low-energy plasma electrolytic oxidation(LePEO)technique is developed to simultaneously improve energy efficiency and anti-corrosion.Ionic liquids(1-butyl-3-methylimidazole tetrafluoroborate(BmimBF_(4)))as sustainable corrosion inhibitors are chosen to investigate the corrosion inhibition behavior of ionic liquid(ILs)during the LePEO process for LA91 magnesium-lithium(Mg-Li)alloy.Results show that the ionic liquid BmimBF_(4)participates in the LePEO coating formation process,causing an increment in coating thickness and surface roughness.The low conductivity of the ionic liquid is responsible for the voltage and breakdown voltage increases during the LePEO with IL process(LePEO-IL).After adding BmimBF_(4),corrosion current density decreases from 1.159×10^(−4)A·cm^(−2)to 8.143×10^(−6)A·cm^(−2).The impedance modulus increases to 1.048×10^(4)Ω·cm^(−2)and neutral salt spray remains intact for 24 h.The superior corrosion resistance of the LePEO coating assisted by ionic liquid could be mainly attributed to its compact and thick barrier layer and physical absorption of ionic liquid.The ionic liquid-assisted LePEO technique provides a promising approach to reducing energy consumption and improving film performance.

Phosphotungstic acid ionic liquid for efficient photocatalytic desulfurization:Synthesis,application and mechanism

An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.

Ionic Liquid-Enhanced Assembly of Nanomaterials for Highly Stable Flexible Transparent Electrodes

The controlled assembly of nanomaterials has demon-strated significant potential in advancing technological devices.However,achieving highly efficient and low-loss assembly technique for nanomate-rials,enabling the creation of hierarchical structures with distinctive func-tionalities,remains a formidable challenge.Here,we present a method for nanomaterial assembly enhanced by ionic liquids,which enables the fabrication of highly stable,flexible,and transparent electrodes featuring an organized layered structure.The utilization of hydrophobic and non-volatile ionic liquids facilitates the production of stable interfaces with water,effectively preventing the sedimentation of 1D/2D nanomaterials assembled at the interface.Furthermore,the interfacially assembled nanomaterial monolayer exhibits an alternate self-climbing behavior,enabling layer-by-layer transfer and the formation of a well-ordered MXene-wrapped silver nanowire network film.The resulting composite film not only demonstrates exceptional photoelectric performance with a sheet resistance of 9.4Ωsq^(-1) and 93%transmittance,but also showcases remarkable environmental stability and mechanical flexibility.Particularly noteworthy is its application in transparent electromagnetic interference shielding materials and triboelectric nanogenerator devices.This research introduces an innovative approach to manufacture and tailor functional devices based on ordered nanomaterials.

Ionic liquid derived electrocatalysts for electrochemical water splitting

Hydrogen production from electrochemical water splitting is a promising strategy to generate green energy,which requires the development of efficient and stable electrocatalysts for the hydrogen evolution reaction and the oxygen evolution reaction(HER and OER).Ionic liquids(ILs)or poly(ionic liquids)(PILs),containing heteroatoms,metal-based anions,and various structures,have been frequently involved as precursors to prepare electrocatalysts for water splitting.Moreover,ILs/PILs possess high conductivity,wide electrochemical windows,and high thermal and chemical stability,which can be directly applied in the electrocatalysis process with high durability.In this review,we focus on the studies of ILs/PILs-derived electrocatalysts for HER and OER,where ILs/PILs are applied as heteroatom dopants and metal precursors to prepare catalysts or are directly utilized as the electrocatalysts.Due to those attractive properties,IL/PIL-derived electrocatalysts exhibit excellent performance for electrochemical water splitting.All these accomplishments and developments are systematically summarized and thoughtfully discussed.Then,the overall perspectives for the current challenges and future developments of ILs/PILs-derived electrocatalysts are provided.

Fixation of CO_2 by electrocatalytic reduction to synthesis of dimethyl carbonate in ionic liquid using effective silver-coated nanoporous copper composites

With high surface area,open porosity and high efficiency,a catalyst was prepared and firstly employed in electrocatalytic reduction of CO2 and electrosynthesis of dimethyl carbonate（DMC）.The electrochemical property for electrocatalytic reduction of CO2 in ionic liquid was studied by cyclic voltammogram（CV）.The effects of various reaction variables like temperature,working potential and cathode materials on the electrocatalytic performance were also investigated.80%yield of DMC was obtained under the optimal reaction conditions.

Depolymerization of polyamide 6 in hydrophilic ionic liquids

Polyamide 6 underwent an efficient depolymerization in hydrophilic ionic liquids under microwave irradiation at 300C. The depolymerization completed within 60 min. Caprolactam was readily separated by simple extraction procedure and the ionic liquids were recovered and reused for several times. Addition of catalytic amounts of DMAP(N,N-dimethylaminopyridine) promoted the depolymerization effectively.The present improved procedure provides a method to avoid direct distillation procedure, which consumes energy for the separation of caprolactam from ionic liquids. Although some contamination of ionic liquids was observed, the present procedure provides a new possibility for the use of ionic liquids for plastic chemical recycling from the viewpoint of development of an energy-saving methodology. Use of solubility switchable ionic liquids is also examined to explore a possibility for better separation although depolymerization did not work well.

Concentration control of volatile organic compounds by ionic liquid absorption and desorption

Volatile organic compounds(VOCs)are difficult to be eliminated safely and effectively because of their large concentration fluctuations.Thus,maintaining a stable concentration of VOCs is a significant study.In this research,H2O,Tween-80,[Emim]BF4,[Emim]PF6,and[Hnmp]HSO4 were applied to absorb and desorb simulated VOCs.The ionic liquid[Emim]BF4 demonstrated the best performance and was thus selected for further experiments.As the ionic liquid acted as a buffer,the toluene concentration with a fluctuation of 2000–20000 mg·m-3 was stabilized at 6000–12000 mg·m-3.Heating distillation(90°C)was highly efficient to recover[Emim]BF4 from toluene.The regenerated[Emim]BF4 could retain its initial absorption capacity even after multiple cycles.Moreover,[Emim]BF4 had the same buffer function on various aromatic hydrocarbons.

Permeability and Selectivity of Sulfur Dioxide and Carbon Dioxide in Supported Ionic Liquid Membranes

Permeabilities and selectivities of gases such as carbon dioxide （CO2）, sulfur dioxide （SO2）, nitrogen （N2） and methane （CH4） in six imidazolium-based ionic liquids （[emim][BF4], [bmim][BF4], [bmim][PF6], [banim][BF4], [bmim][Tf2N] and [emim][CF3SO3]） supported on polyethersulfone microfiltration membranes are investigated in a single gas feed system using nitrogen as the environment and reference component at temperature from 25 to 45℃ and pressure of N2 from 100 to 400 kPa. It is found that SO2 has the highest permeability in the tested supported ionic liquid membranes, being an order of magnitude higher than that of CO2, and about 2 to 3 orders of magnitude larger than those of N2 and CH4. The observed selectivity of SO2 over the two ordinary gas components is also striking. It is shown experimentally that the dissolution and transport of gas components in the supported ionic liquid membranes, as well as the nature of ionic liquids play important roles in the gas permeation. A nonlinear increase of permeation rate with temperature and operation pressure is also observed for all sample gases. By considering the factors that influence the permeabilities and selectivities of CO2 and SO2, it is expected to develop an optimal supported ionic liquid membrane technology for the isolation of acidic gases in the near future.

Separation of ionic liquids from dilute aqueous solutions using the method based on CO_2 hydrates

Ionic liquids （ILs） have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydrate formation. For illustration, the dilute aqueous solutions with concentrations of ILs ranging from 2× 10^-3 mol% to 2×10^-1 mol% were concentrated. The results show that the separation efficiency is very impressive and that the new method is applicable to aqueous solutions of both hydrophobic and hydrophilic ILs. Compared to the literature separation method based on the supercritical CO2, the new method is applicable to lower concentrations, and more importantly, its operation condition is mild.

Design, Optimization and Control of Extractive Distillation for Separation of Ethyl Acetate-Ethanol-Water Mixture Using Ionic Liquids

In this work, the process simulation of pressure-swing distillation(PSD) and extractive distillation(ED) using ionic liquid(IL) 1-butyl-3-methylimidazolium acetate([bmim][OAc]) as the entrainer for separation of ethyl acetateethanol-water mixture is performed. The design parameters of the two distillation processes are optimized with the minimum total annual cost(TAC) serving as the objective function. The results show that the TAC saving of ED process is 35.27% in comparison with that of PSD process in the case of achieving the same purity and yield of ethyl acetate.In addition, the dynamic controllability of ED process is further studied. The traditional two-point temperature control structure is proposed for the ED process, and it works pretty well while taking into account the disturbances in both feed rate and feed composition.

In-situ generated ionic liquid catalyzed aldol condensation of trioxane with ester in mild homogeneous system

α, β-unsaturated esters were often synthesized from aldehydes and esters in the presence of strong organic base that was very sensitive to air and moisture via aldol reaction. Trioxane was very useful C1 resource, however, the decomposition of it was always the challenging problem that facing researchers. Herein, a novel synthetic methodology for α, β-unsaturated ester preparation from trioxane and ester with mild catalysis of generated ammonium trifluoromethanesulfonate ionic liquid. The enolization of ester as well as the decomposition of trioxane could proceed easily in the presence of boryl trifluoromethanesulfonate and amine at 20–25℃. Then the enolate and decomposed formaldehyde occurs aldol reaction to form α, β-unsaturated ester. With this strategy, the yield and selectivity of product from various substrates including aliphatic esters,lactones and thioester could reach up to 85.2% and 90.1%.

Facile synthesis of thiourea derivatives in ionic liquid

The synthesis of cinnamoyi thiourea derivatives from cinnamoyl isothiocyanate （CIT） with substituted aniline （RC6H4NH2） was investigated in the mostly used ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [Bmim][BF4]. Significant enhancements in reactivity, yield and reaction rate were achieved. The products could be recovered by simple filtration. [Bmlm] [BF4] could be recycled simply by removing water under vacuum and reused at least 9 times without significant decrease in activity.

Anionic structural effect in liquid–liquid separation of phenol from model oil by choline carboxylate ionic liquids

Phenolic compounds exist in crude oil as pollutants, and their removal is vital important for the refining and further application of oils. In traditional separation approaches, strong acid and strong base have to be used to remove these compounds, which may cause serious environmental problems. In this work, 19 kinds of cholinium ionic liquids have been developed to separate phenol from model oil by liquid–liquid extraction. Structural effect of anions of the ionic liquids in the separation is systematically investigated. It is found that depending on the chemical structure of ionic liquids, phenol can be removed from toluene with single-step removal efficiency from 86 to 99% under optimal conditions. The type of substituent groups and the-CH_2 number between two carboxylates have obvious effect on the removal efficiency, and more hydrophilic ionic liquids have a stronger extraction performance for phenol. Furthermore, thermodynamic,^(13) C NMR,~1 H NMR and density functional theory calculations have been performed to characterize the extraction process and to understand the extraction mechanism. It is shown that the extraction of phenol from oil to ionic liquid is a favorable process, and this process is mainly driven by enthalpy change. The formation of the hydrogen bond between anion of the ionic liquid and-OH of phenol is the main driving force for the extraction of phenol from oil to the ionic liquids.

Polyoxometalate-based silica-supported ionic liquids for heterogeneous oxidative desulfurization in fuels

With the aim of deep desulfurization, silica-supported polyoxometalate-based ionic liquids were successfully prepared by a one-pot hydrothermal process and employed in heterogeneous oxidative desulfurization of various sulfur compounds. The compositions and structures of the hybrid samples were characterized by various methods such as FT-IR, XPS, Raman,UV–Vis, wide-angle XRD and N2adsorption–desorption. The experimental results indicated that the hybrid materials presented a high dispersion of tungsten species and excellent catalytic activity for the removal of 4,6-dimethyldibenzothiophene without any organic solvent as extractant, and the sulfur removal could reach 100.0% under mild conditions.The catalytic performance on various substrates was also investigated in detail. After cycling seven cycles, the sulfur removal of the heterogeneous system still reached 93.0%. The GC-MS analysis results demonstrated that the sulfur compound was first adsorbed by the catalyst and subsequently oxidized to its corresponding sulfone.