Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids

The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.

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.

Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.

Ionic liquids as the effective technology for enhancing transdermal drug delivery: Design principles, roles, mechanisms, and future challenges

Ionic liquids (ILs) have been proven to be an effective technology for enhancing drug transdermal absorption. However, due to the unique structural components of ILs, the design of efficient ILs and elucidation of action mechanisms remain to be explored. In this review, basic design principles of ideal ILs for transdermal drug delivery system (TDDS) are discussed considering melting point, skin permeability, and toxicity, which depend on the molar ratios, types, functional groups of ions and inter-ionic interactions. Secondly, the contributions of ILs to the development of TDDS through different roles are described: as novel skin penetration enhancers for enhancing transdermal absorption of drugs;as novel solvents for improving the solubility of drugs in carriers;as novel active pharmaceutical ingredients (API-ILs) for regulating skin permeability, solubility, release, and pharmacokinetic behaviors of drugs;and as novel polymers for the development of smart medical materials. Moreover, diverse action mechanisms, mainly including the interactions among ILs, drugs, polymers, and skin components, are summarized. Finally, future challenges related to ILs are discussed, including underlying quantitative structure-activity relationships, complex interaction forces between anions, drugs, polymers and skin microenvironment, long-term stability, and in vivo safety issues. In summary, this article will promote the development of TDDS based on ILs.

Complete degradation of high-loaded phenol using tungstate-based ionic liquids with long chain substituent at mild conditions

Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

Enhancing CO_(2) transport with plasma-functionalized ionic liquid membranes

The ionic liquid(IL) 1-butyl-3-methylimidazolium tetrafluoroborate treated with radiofrequency plasma is proposed for functionalization and immobilization on polyethersulfone supports to form supported ionic liquid membranes for CO_(2) separation.The effects of treatment time and transmembrane pressure difference on CO_(2) permeance were evaluated.The best gas permeation performance was obtained with a treatment time of 10 min and the transmembrane pressure difference was 0.25 MPa.Characterization of the materials by Fourier transform infrared spectroscopy,x-ray photoelectron spectroscopy and nuclear magnetic resonance spectroscopy demonstrates that the IL is grafted with carboxyl groups and deprotonated through plasma treatment.A preliminary mechanism for the plasma treatment and facilitated transport of CO_(2)has been proposed on this basis.

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-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

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.

Experimental study of the effect of gas discharge on ionic liquid electrospray

Ionic liquid electrospray(ILE) in an atmospheric environment is often accompanied by the gas discharge phenomenon. It interferes with the normal operation of the electrospray and the measurement of experimental parameters. In this study, electrospray experiments were conducted on the ionic liquid EMI-BF4. The observations revealed that the operating modes of the ionic liquid depend on the voltage polarity at high voltages. Additionally, a correspondence between the operating mode of ILE and the current signal in the circuit was established. The shape of the liquid cone formed at the needle tip bore a striking resemblance to the plume of corona discharge, suggesting that the motion trajectory of electrons influenced the curvature of the liquid cone. Steamer theory provided a clear explanation for the change in curvature as the voltage increased.

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.

Experimental investigation of the polarityswitching process with different bipolar ionic liquid thruster operating frequencies

The bipolar ionic liquid thruster employs ionic liquid as a propellant to discharge positively and negatively charged high-energy particles under an alternating current(AC)power source,effectively suppressing electrochemical reaction and ensuring charge neutrality.Determining an optimal AC supply power source frequency is critical for sustained stable thruster operation.This study focuses on the emission characteristics of the ionic liquid thruster under varied AC conditions.The AC power supply was set within the frequency range of 0.5-64 Hz,with eight specific frequency conditions selected for experimentation.The experimental results indicate that the thruster operates steadily within a voltage range of±1470 to±1920 V,with corresponding positive polarity current ranging from 0.41 to 4.91μA and negative polarity current ranging from−0.49 to−4.10μA.During voltage polarity switching,an emission delay occurs,manifested as a prominent peak signal caused by circuit capacitance characteristics and a minor peak signal resulting from liquid droplets.Extended emission test was conducted at 16 Hz,demonstrating approximately 1 h and 50 min of consistent emission before intermittent discharge.These findings underscore the favorable impact of AC conditions within the 8-16 Hz range on the self-neutralization capability of the ionic liquid thruster.

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.

Revealing structure correlation between ionic liquid and metal-organic framework matrix

Solid-state batteries are rising rapidly in response to the fast-increasing energy demand.Metal-organic framework(MOF) loaded with ionic liquids has brought new opportunities for solid-state batteries owing to its good interfacial compatibility and high ionic conductivity. MOF-808 is selected to be filled with Li-contained ionic liquid for structure and ion dynamics investigation using nuclear magnetic resonance(NMR) and X-ray diffraction.This study finds that the introduced ionic liquid would partially soften the matrix of MOF-808 and thus yield amorphous phase. By selective isotope replacement under cycling symmetric ^(6)Li metal cell, Li^(+)ion is observed to mainly go cross ionic liquid in the open channel of matrix under potential polarization.

The opportunities and challenges of ionic liquids in perovskite solar cells

Metal halide perovskite solar cells(PSCs)have shown great potential to become the next generation of photovoltaic devices due to their simple fabrication techniques,low cost,and soaring power conversion efficiency(PCE).However,mismatched with the quickly updated PCEs,the improvement of device stability is challenging and still remains a critical hurdle in the path to commercialization.Recently,ionic liquids(ILs)have been found to play multiple roles in obtaining efficient and stable PSCs.These ILs usually consist of large organic cations and organic or inorganic anions,which have weak electrostatic attraction and are generally liquid at around 100℃.ILs are almost non-volatile,non-flammable,with high ionic conductivity and excellent thermal and electrochemical stability.The roles of ILs in PSCs vary with their composition,that is,the types of anions and cations.In this review,we summarize the roles of anions and cations in terms of precursor solutions,additives,perovskite/charge transport layer interface engineering,and charge transport layers.This article aims to set up a structure–property-stability-performance correlations conferred by the IL in PSC and provide assistance for the anion and cation selection for improving the quality of perovskite film,optimizing interface contact,reducing defect states,and improving charge extraction and transport characteristics.Finally,the application of IL in PSCs is discussed and prospected.

Molecular design and applications of a nanostructure green Tripodal surface active ionic liquid in enhanced oil recovery: Interfacial tension reduction, wettability alteration, and emulsification

Surface active ionic liquids (SAILs) are considered as prominent materials in enhanced oil recovery thanks to their high interfacial activity. This study reports the preparation and applications of a nanostructure Tripodal imidazolium SAIL as an environmentally-friendly substitute to the conventional surfactants. The product has a star-like molecular structure centered by a triazine spacer, namely [(C_(4)im)_(3)TA][Cl_(3)], prepared by a one-step synthesis method and characterized with FT-IR, NMR, XRD, and SEM analysis methods. The interfacial tension of the system was decreased to about 78% at critical micelle concentration of less than 0.08 mol·dm^(−3). Increasing temperature, from 298.2 to 323.2 K, improved this capability. The solid surface wettability was changed from oil-wet to water-wet and 80% and 77% stable emulsions of crude oil–aqueous solutions were created after one day and one week, respectively. Compared to the Gemini kind homologous SAILs, the superior effects of the Tripodal SAIL were revealed and attributed to the strong hydrophobic branches in the molecule. The Frumkin adsorption isotherm precisely reproduced the generated IFT data, and accordingly, the adsorption and thermodynamic parameters were determined.

Ionic liquids-SBA-15 hybrid catalysts for highly efficient and solvent-free synthesis of diphenyl carbonate

Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.

Synthesis and characterization of a 1,3-dibutylimidazolium azide([BBIm][N_(3)]) : A promising green energetic ionic liquid

In the pursuit of advancing imidazolium-based energetic ionic liquids (EILs),the current study is devoted to the synthesis and characterization of 1,3-dibutyl-imidazolium azide ([BBIm][N_(3)]),as a novel member in this ionic liquids class.The chemical structure of this EIL was rigorously characterized and confirmed using FTIR spectroscopy,1D,and 2D-NMR analyses.The thermal behavior assessment was conducted through DSC and TGA experiments.DSC analysis revealed an endothermic glass transition at T_(g)=-61℃,followed by an exothermic degradation event at T_(onset)=311℃.Similarly,TGA thermograms exhibited a one-stage decomposition process resulting in 100% mass loss of the sample.Furthermore,the short-term thermal stability of the azide EIL was investigated by combining the non-isothermal TGA data with the TAS,it-KAS,and VYA/CE isoconversional kinetic approaches.Consequently,the Arrhenius parameters(E_(a)=154 kJ·mol^(-1),Log(A/s^(-1))=11.8) and the most probable reaction model g(a) were determined.The observed high decomposition temperatures and the significantly elevated activation energy affirm the enhanced thermal stability of the modified EIL.These findings revealed that[BBIm][N_(3)]EIL can be a promising candidate for advanced energetic material application.

Separation of lithium and nickel using ionic liquids and tributyl phosphate

With the vigorous development of the electronics industry,the consumption of lithium continues to increase,and more lithium needs to be mined to meet the development of the industry.The content of lithium in the solution is much higher than that of minerals,but the interference of impurity ions increases the difficulty of extracting lithium ions.Therefore,we prepared an imidazole-based ionic liquid(1-butyl-3-methylImidazolium bis(trifluoromethyl sulfonyl)imide)(IL)for efficient lithium extraction from aqueous solutions by solvent extraction.Using an extraction consisting of 10%IL,85% tributyl phosphate(TBP),and 5% dichloroethane and an organic to aqueous phase ratio(O/A)of 2/1,over 64.23% of Li were extracted,and the extraction rate after five-stage extraction could reach more than 96%.The addition of ammonium ions to the solution inhibited the extraction of Ni,and the separation coefficient between lithium and nickel approached infinity,showing a very perfect separation effect.Fouriertransform infrared spectroscopy and slope methods were used to analyze the changes that occurred during extraction,revealing possible extraction mechanisms.In addition,the LiCl solution generated during the preparation of ionic liquids was mixed with the stripping solution,and the battery-grade lithium carbonate was prepared by Na_(2)CO_(3) precipitation,with a purity of 99.74%.This study provides an efficient and sustainable strategy for recovering lithium from the solution.