Electrorefining of aluminum in urea-imidazole chloride-aluminum chloride ionic liquids

The electrochemical behavior of Al(Ⅲ)in urea-1-butyl-3-methylimidazolium chloride-aluminum chloride(urea-BMIC-AlCl_(3))ionic liquids,and the effect of potential and temperature on the characterization of cathode products,current efficiency and energy consumption of aluminum electrorefining have been investigated.Cyclic voltammetry showed that the electrochemical reduction of Al(Ⅲ)was a one-step three-electron-transfer irreversible reaction,and the electrochemical reaction was controlled by diffusion.The diffusion coefficient of Al(Ⅲ)in urea-BMIC-AlCl_(3)ionic liquids at 313 K was 1.94×10^(−7)cm^(2)/s.The 7075 aluminum alloy was used as an anode for electrorefining,and the cathode products were analyzed by XRD,SEM and EDS.The results from XRD analysis indicated that the main phase of the cathode products was aluminum.The results from SEM and EDS characterization revealed that the cathode product obtained by electrorefining−1.2 V(vs.Al)was dense and uniform,and the mass fraction of aluminum decreased from 99.61%to 99.10%as the experimental temperature increased from 313 K to 333 K.In this work,the optimum experimental conditions were−1.2 V(vs.Al)and 313 K.At this time,the cathode current efficiency was 97.80%,while the energy consumption was 3.72 kW·h/kg.

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.

Effects of ionic liquids on the vaporeliquid equilibrium of 1,3,5-trioxaneewater system at 101.3 kPa

Increasing the 1,3,5-trioxane(TOX)concentration in the equilibrated vapor phase of TOXeH_(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 TOXeH_(2)O system.The vaporeliquid equilibrium of TOXeH_(2)O 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.

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.

Design of dual-functional protic porous ionic liquids for boosting selective extractive desulfurization

Porous ionic liquids have demonstrated excellent performance in the field of separation,attributed to their high specific surface area and efficient mass transfer.Herein,task-specific protic porous ionic liquids(PPILs)were prepared by employing a novel one-step coupling neutralization reaction strategy for extractive desulfurization.The single-extraction efficiency of PPILs reached 75.0%for dibenzothiophene.Moreover,adding aromatic hydrocarbon interferents resulted in a slight decrease in the extraction efficiency of PPILs(from 45.2%to 37.3%,37.9%,and 33.5%),indicating the excellent extraction selectivity of PPILs.The experimental measurements and density functional theory calculations reveal that the surface channels of porous structures can selectively capture dibenzothiophene by the stronger electrophilicity(Eint(HS surface channel/DBT)=-39.8 kcal mol^(-1)),and the multiple extraction sites of ion pairs can effectively enrich and transport dibenzothiophene from the oil phase into PPILs throughπ...π,C-H...πand hydrogen bonds interactions.Furthermore,this straightforward synthetic strategy can be employed in preparing porous liquids,offering new possibilities for synthesizing PPILs with tailored functionalities.

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.

Direct observation of ordered-disordered structural transition of MoS_(2)-confined ionic liquids

Ionic liquids(ILs)are an emerging class of media of fundamental importance for chemical engineering,especially due to their interaction with solid surfaces.Here,we explore the growth phenomenon of surface-confined ILs and reveal a peculiar structural transition behavior from order to disorder above a threshold thickness.This behavior can be explained by the variation of interfacial forces with increasing distance from the solid surface.Direct structural observation of different ILs highlights the influence of the ionic structure on the growth process.Notably,the length of the alkyl chain in the cation is found to be a determining factor for the ordering trend.Also,the thermal stability of surface-confined ILs is investigated in depth by controlling annealing treatments.It is found that the ordered monolayer ILs exhibit high robustness against high temperatures.Our findings provide new perspectives on the properties of surface-confined ILs and open up potential avenues for manipulating the structures of nanometer-thick IL films for various applications.

Universal basis underlying temperature, pressure and size induced dynamical evolution in metallic glass-forming liquids

The dramatic temperature-dependence of liquids dynamics has attracted considerable scientific interests and efforts in the past decades, but the physics of which remains elusive. In addition to temperature, some other parameters, such as pressure, loading and size, can also tune the liquid dynamics and induce glass transition, which makes the situation more complicated. Here, we performed molecular dynamics simulations for Ni_(50)Zr_(50) bulk liquid and nanodroplet to study the dynamics evolution in the complex multivariate phase space, especially along the isotherm with the change of pressure or droplet size. It is found that the short-time Debye–Waller factor universally determines the long-time relaxation dynamics no matter how the temperature, pressure or size changes. The basic correlation even holds at the local atomic scale. This finding provides general understanding of the microscopic mechanism of dynamic arrest and dynamic heterogeneity.

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.

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.

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.

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.

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.

Modeling of liquid film thickness around Taylor bubbles rising in vertical stagnant and co-current slug flowing liquids

The hydrodynamic study of the liquid film around Taylor bubbles in slug flow has great significance for understanding parallel flow and interaction between Taylor bubbles.The prediction models for liquid film thickness mainly focus on stagnant flow,and some of them remain inaccurate performance.However,in the industrial process,the slug flow essentially is co-current flow.Therefore,in this paper,the liquid film thickness is studied by theoretical analysis and experimental methods under two conditions of stagnant and co-current flow.Firstly,under the condition of stagnant flow,the present work is based on Batchelor's theory,and modifies Batchelor's liquid film thickness model,which effectively improves its prediction accuracy.Under the condition of co-current flow,the prediction model of average liquid film thickness in slug flow is established by force and motion analysis.Taylor bubble length is introduced into the model as an important parameter.Dynamic experiments were carried out in the pipe with an inner diameter of 20 mm.The liquid film thickness,Taylor bubble velocity and length were measured by distributed ultrasonic sensor and intrusive cross-correlation conductivity sensor.Comparing the predicted value of the model with the measured results,the relative error is controlled within 10%.

A simple hydroxypyridine ionic liquids for conversion of CO_(2)into quinazoline-2,4(1H,3H)-diones under atmospheric conditions

The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high efficiency catalytic system with environmentally benign characteristic are important determinants.In this work,protic ionic liquids[TMG][2-OPy]were prepared via one-step neutralization between 1,1,3,3-tetramethylguanidine and 2-hydroxypyridine,applying to the domain of synthesizing quinzoline-2,4(1 H,3H)-diones from CO_(2)and 2-aminobenzontiles without any solvent or metal,achieving the yield of 97%at 90℃for 8 h under atmospheric.A series of substrates with good to acceptable yield were detected,revealing the generality and universality of the catalyst.Furthermore,the system could be facilely reused for at least six runs,retaining the yield of 94%.A preliminary kinetic equation is calculated with the activation energy of 68 kJ·mol^(-1),and a plausible reaction mechanism was put forward.This study highlights that the[TMG][2-OPy]enables to activate CO_(2)carboxylation 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.

液氮冻结和冻融条件下煤体力学特性及裂隙演化教学实验设计

该文设计了液氮冻结煤岩实验装置,并进行了液氮冻结和冻融条件下煤体力学特性实验,研究了液氮冻结时间和冻融次数对煤体力学强度及裂隙演化的影响规律,定量分析了液氮冷浸对煤体力学特征的影响。通过基于机理分析的实验教学拓展延伸,能够使学生从原理层面分析实验结果,学习宏微观结合的分析方法,加深对实验课程的理解,提高创新能力,开拓学术视野。

液晶包层波导技术研究进展

液晶包层波导以波导为载体、以液晶为工作物质,包层中的液晶通过倏逝波调控芯层中的波导模式。相比于传统液晶器件,液晶包层波导能够巧妙解耦光线调制距离与液晶层厚度,并基于表面层液晶作用显著降低液晶回弹时间,具有调制幅度大、响应速度快的优势。本文综述了液晶包层波导技术在光束扫描、傅里叶变换光谱领域的研究进展,并展望了液晶包层波导技术在可重构光子器件领域的应用前景。不同的宏观应用表现均源于液晶包层对波导模式的微观调控。凭借独特的工作方式,液晶包层波导赋予了宏观应用新的技术优势。本综述为新型液晶光束调控方法提供一种重要的研究思路。

一种适于脉动条件的气液分离器的设计与研究

文中针对在流量脉动条件下,无罩、圆柱状、“柱+锥”状稳涡罩对气液分离器的分离性能及流场特性产生的影响,进行了数值模拟和试验研究,提出了旋流场脉动衰减程度评价指标———脉动衰减率(ηp),其值大小与脉动衰减性能成反比。研究结果显示:在流量脉动条件下,“柱+锥”状稳涡罩对于提高旋流场稳定性的能力最为显著,脉动衰减率为0.01028,分离效率最高可达95.15%;同时,运用高速摄像技术对两相流场中气核运动及变化形态进行可视化观测,掌握了基于流量脉动条件下,旋流场内气核的运移规律,并将其划分为4个阶段(断续阶段、汇聚阶段、融合阶段、最终阶段),发现“柱+锥”状稳涡罩旋流器的气核向中心轴线聚集趋势显著,形成具有向上运动形态的空气柱,对旋流场内脉动流有明显的抑制作用。

车用液氢气瓶快充过程数值研究

车用液氢气瓶加注过程中,因加注速度快且气瓶容积小,极易造成过充现象,导致安全事故发生。针对设有气包防过充装置的车载液氢气瓶建立三维对称模型,采用CFD方法对气瓶快速加注过程开展数值仿真。分析了开孔孔径、加注速率、初始充满率和防过充装置容积对防过充装置性能的影响规律。结果表明:开孔孔径是影响防过充装置性能的主要因素,其限制了液体的流通能力;采用6 mm孔径和初始充装量为50%的状况下,充装结束后气瓶都将过充,最大充装率可达98.4%;采用大容积的防过充装置可以为气瓶预留更多的气相安全空间,但同时也会导致充装量不足等问题,当防过充装置容积为100 L时,最终充装量仅有77.2%。