The absorption of CO_(2)is of importance in carbon capture,utilization,and storage technology for greenhouse gas control.In the present work,we clarified the mechanism of how metal-based ionic liquids (MBILs),Bmim[XCl...The absorption of CO_(2)is of importance in carbon capture,utilization,and storage technology for greenhouse gas control.In the present work,we clarified the mechanism of how metal-based ionic liquids (MBILs),Bmim[XCl_(n)]_(m)(X is the metal atom),enhance the CO_(2)absorption capacity of ILs via performing molecular dynamics simulations.The sparse hydrogen bond interaction network constructed by CO_(2)and MBILs was identified through the radial distribution function and interaction energy of CO_(2)-ion pairs,which increase the absorption capacity of CO_(2)in MBILs.Then,the dynamical properties including residence time and self-diffusion coefficient confirmed that MBILs could also promote the diffusion process of CO_(2)in ILs.That's to say,the MBILs can enhance the CO_(2)absorption capacity and the diffusive ability simultaneously.Based on the analysis of structural,energetic and dynamical properties,the CO_(2)absorption capacity of MBILs increases in the order Cl^-→[ZnCl_(4)]^(2-)→[CuCl_(4)]^(2-)→[CrCl_(4)]^-→[FeCl_(4)]^-,revealing the fact that the short metal–Cl bond length and small anion volume could facilitate the performance of CO_(2)absorbing process.These findings show that the metal–Cl bond length and effective volume of the anion can be the effective factors to regulate the CO_(2)absorption process,which can also shed light on the rational molecular design of MBILs for CO_(2)capture and other key chemical engineering processes,such as IL-based gas sensors,nano-electrical devices and so on.展开更多
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 prod...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.展开更多
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...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.展开更多
To conduct extensive research on the application of ionic liquids as collectors in mineral flotation,ethanol(EtOH)was used as a solvent to dissolve hydrophobic ionic liquids(ILs)to simplify the reagent regime.Interest...To conduct extensive research on the application of ionic liquids as collectors in mineral flotation,ethanol(EtOH)was used as a solvent to dissolve hydrophobic ionic liquids(ILs)to simplify the reagent regime.Interesting phenomena were observed in which EtOH exerted different effects on the flotation efficiency of two ILs with similar structures.When EtOH was used to dissolve 1-dodecyl-3-methylimidazolium chloride(C12[mim]Cl)and as a collector for pure quartz flotation tests at a concentration of 1×10^(−5)mol·L^(−1),quartz recovery increased from 23.77%to 77.91%compared with ILs dissolved in water.However,quartz recovery of 1-dodecyl-3-methylim-idazolium hexafluorophosphate(C12[mim]PF6)decreased from 60.45%to 24.52%under the same conditions.The conditional experi-ments under 1×10^(−5)mol·L^(−1)ILs for EtOH concentration and under 2vol%EtOH for ILs concentration confirmed this difference.After being affected by EtOH,the mixed ore flotation tests of quartz and hematite showed a decrease in the hematite concentrate grade and re-covery for the C12[mim]Cl collector,whereas the hematite concentrate grade and recovery for the C12[mim]PF6 collector increased.On the basis of these differences and observations of flotation foam,two-phase bubble observation tests were carried out.The EtOH promoted the foam height of two ILs during aeration.It accelerated static froth defoaming after aeration stopped,and the foam of C12[mim]PF6 de-foaming especially quickly.In the discussion of flotation tests and foam observation,an attempt was made to explain the reasons and mechanisms behind the diverse phenomena using the dynamic surface tension effect and solvation effect results from EtOH.The solva-tion effect was verified through Fourier transform infrared(FT-IR),X-ray photoelectron spectroscopy(XPS),and Zeta potential tests.Al-though EtOH affects the adsorption of ILs on the ore surface during flotation negatively,it holds an positive value of inhibiting foam mer-ging during flotation aeration and accelerating the defoaming of static foam.And induce more robust secondary enrichment in the mixed ore flotation of the C12[mim]PF6 collector,facilitating effective mixed ore separation even under inhibitor-free conditions.展开更多
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...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.展开更多
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...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.展开更多
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...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.展开更多
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 act...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.展开更多
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...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.展开更多
Several metal-based ionic liquids（ILs） were synthesized and used as extractants for the desulfurization of dibenzothiophene（DBT） in simulated fuel oil.The effects of several anion and metal ions,n（ILs）/n（metal...Several metal-based ionic liquids（ILs） were synthesized and used as extractants for the desulfurization of dibenzothiophene（DBT） in simulated fuel oil.The effects of several anion and metal ions,n（ILs）/n（metal） as mole ratio,V（IL）/V（oil） and extractive times on the removal ratio of DBT were investigated in detail.The results showed that[BMIM]HSO4/FeCl3（BMIM was short for l-butyl-3-methyl imidazole）was superior to the other ILs for the extractive desulfurization.A total of 100%of DBT was removed at room temperature in 5 min with V[BMIM]HSO4/Fecl3/Voil = 1：1.The extractive activity of[BMIM]HSO4/FeCl3 IL did not change almost after five runs.Extractive desulfurization of different sulfur compounds and commercial diesel fuel oil were also examined.The removal ratios of the sulfur compounds as the reaction substrates were all over 90%and the sulfur content of commercial diesel oil decreased to120 ppm from 12,400 ppm.展开更多
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 sustainab...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.展开更多
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 qu...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.展开更多
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 cr...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.展开更多
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...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.展开更多
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 me...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.展开更多
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...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.展开更多
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 co...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.展开更多
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 parame...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.展开更多
Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium ...Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.展开更多
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 th...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.展开更多
基金financial support of the National Science Foundation of China(No.21808220)。
文摘The absorption of CO_(2)is of importance in carbon capture,utilization,and storage technology for greenhouse gas control.In the present work,we clarified the mechanism of how metal-based ionic liquids (MBILs),Bmim[XCl_(n)]_(m)(X is the metal atom),enhance the CO_(2)absorption capacity of ILs via performing molecular dynamics simulations.The sparse hydrogen bond interaction network constructed by CO_(2)and MBILs was identified through the radial distribution function and interaction energy of CO_(2)-ion pairs,which increase the absorption capacity of CO_(2)in MBILs.Then,the dynamical properties including residence time and self-diffusion coefficient confirmed that MBILs could also promote the diffusion process of CO_(2)in ILs.That's to say,the MBILs can enhance the CO_(2)absorption capacity and the diffusive ability simultaneously.Based on the analysis of structural,energetic and dynamical properties,the CO_(2)absorption capacity of MBILs increases in the order Cl^-→[ZnCl_(4)]^(2-)→[CuCl_(4)]^(2-)→[CrCl_(4)]^-→[FeCl_(4)]^-,revealing the fact that the short metal–Cl bond length and small anion volume could facilitate the performance of CO_(2)absorbing process.These findings show that the metal–Cl bond length and effective volume of the anion can be the effective factors to regulate the CO_(2)absorption process,which can also shed light on the rational molecular design of MBILs for CO_(2)capture and other key chemical engineering processes,such as IL-based gas sensors,nano-electrical devices and so on.
基金Project(52004062)supported by the National Natural Science Foundation of ChinaProject(2020-MS-084)supported by the Natural Science Foundation of Liaoning Province,ChinaProject(N2125014)supported by the Fundamental Research Funds for the Central Universities,China。
文摘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.
基金supported by the National Natural Science Foundation of China(22125802,22078010).
文摘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.
基金supported by the National Natural Science Foundation of China(No.51874221)the Open Foundation of Guangxi Key Laboratory of Processing for Nonferrous Metals and Featured Materials,Guangxi University(No.2022GXYSOF 11).
文摘To conduct extensive research on the application of ionic liquids as collectors in mineral flotation,ethanol(EtOH)was used as a solvent to dissolve hydrophobic ionic liquids(ILs)to simplify the reagent regime.Interesting phenomena were observed in which EtOH exerted different effects on the flotation efficiency of two ILs with similar structures.When EtOH was used to dissolve 1-dodecyl-3-methylimidazolium chloride(C12[mim]Cl)and as a collector for pure quartz flotation tests at a concentration of 1×10^(−5)mol·L^(−1),quartz recovery increased from 23.77%to 77.91%compared with ILs dissolved in water.However,quartz recovery of 1-dodecyl-3-methylim-idazolium hexafluorophosphate(C12[mim]PF6)decreased from 60.45%to 24.52%under the same conditions.The conditional experi-ments under 1×10^(−5)mol·L^(−1)ILs for EtOH concentration and under 2vol%EtOH for ILs concentration confirmed this difference.After being affected by EtOH,the mixed ore flotation tests of quartz and hematite showed a decrease in the hematite concentrate grade and re-covery for the C12[mim]Cl collector,whereas the hematite concentrate grade and recovery for the C12[mim]PF6 collector increased.On the basis of these differences and observations of flotation foam,two-phase bubble observation tests were carried out.The EtOH promoted the foam height of two ILs during aeration.It accelerated static froth defoaming after aeration stopped,and the foam of C12[mim]PF6 de-foaming especially quickly.In the discussion of flotation tests and foam observation,an attempt was made to explain the reasons and mechanisms behind the diverse phenomena using the dynamic surface tension effect and solvation effect results from EtOH.The solva-tion effect was verified through Fourier transform infrared(FT-IR),X-ray photoelectron spectroscopy(XPS),and Zeta potential tests.Al-though EtOH affects the adsorption of ILs on the ore surface during flotation negatively,it holds an positive value of inhibiting foam mer-ging during flotation aeration and accelerating the defoaming of static foam.And induce more robust secondary enrichment in the mixed ore flotation of the C12[mim]PF6 collector,facilitating effective mixed ore separation even under inhibitor-free conditions.
基金financially supported by the National Natural Science Foundation of China (Nos.22078135,21808092,21978119,22202088)。
文摘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.
基金supported by the National Natural Science Foundation of China(22168002,22108070,21878078)the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)+2 种基金the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。
文摘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.
基金supported by the National Key Research and Development Program of China(2021YFB3802600)the National Natural Science Foundation of China(22278396,22378392,22178344)+1 种基金the Youth Innovation Promotion Association CAS(Y2021022)the Open Research Fund of State Key Laboratory of Mesoscience and Engineering(MESO-23-D17)。
文摘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.
基金funded by the National Natural Science Foundation of China(82273881 and 82304386)Guangdong Basic and Applied Basic Research Foundation(2022A1515110476)+1 种基金the Open Fund of Guangdong Provincial Key Laboratory of Infectious Diseases and Molecular Immunopathology(GDKL202214)SUMC Scientiffc Research Initiation Grant(510858046 and 510858056).
文摘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.
基金supported by the National Natural Science Foundation of China(nos.22168012 and 22208070)the Key Laboratory of Carbon-based Energy Molecular Chemical Utilization Technology in Guizhou Province(no.2023008)the Guizhou Province Outstanding Young Scientific and Technological Talents Program(no.YQK2023007).
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.21106032)Hebei University of Science and Technology doctor funding(No.000172)
文摘Several metal-based ionic liquids（ILs） were synthesized and used as extractants for the desulfurization of dibenzothiophene（DBT） in simulated fuel oil.The effects of several anion and metal ions,n（ILs）/n（metal） as mole ratio,V（IL）/V（oil） and extractive times on the removal ratio of DBT were investigated in detail.The results showed that[BMIM]HSO4/FeCl3（BMIM was short for l-butyl-3-methyl imidazole）was superior to the other ILs for the extractive desulfurization.A total of 100%of DBT was removed at room temperature in 5 min with V[BMIM]HSO4/Fecl3/Voil = 1：1.The extractive activity of[BMIM]HSO4/FeCl3 IL did not change almost after five runs.Extractive desulfurization of different sulfur compounds and commercial diesel fuel oil were also examined.The removal ratios of the sulfur compounds as the reaction substrates were all over 90%and the sulfur content of commercial diesel oil decreased to120 ppm from 12,400 ppm.
基金supported by the Natural Science Founda-tion of Beijing(Grant No.2182017,2202017).
文摘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.
基金the financial supports from National Natural Science Foundation of China(22172066,22378176)supported by State Key Laboratory of Heavy Oil ProcessingSupported by Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment,Suzhou University of Science and Technology。
文摘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.
基金This work was supported by the National Natural Science Foundation of China(nos.21988102,and 22305026)the China Postdoctoral Science Foundation(2019M650433).
文摘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.
基金supported by the Natural Science Founda-tion of Chongqing(cstc2021jcyj-msxmX0420)Natural Science Foundation of Sichuan(2023NSFSC0088)。
文摘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.
基金supported by the National Key R&D Program of China ‘Intergovernmental International Scientific and Technological Innovation Cooperation’ (No. 2019YFE0122100)。
文摘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.
基金supported by National Natural Science Foundation of China(21978066)Basic Research Program of Hebei Province for Natural Science Foundation and Key Basic Research Project(18964308D)the Key Program of Natural Science Foundation of Hebei Province(B2020202048).
文摘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.
基金funding of the National Natural Science Foundation of China(no.21776235,no.21376197)the studentship by the Hong Kong Polytechnic University。
文摘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.
基金supported by the National Key Research and Development Program of China(No.2020YFC2201004)National Natural Science Foundation of China(No.12172110)。
文摘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.
基金supported by the National Key Research and Development Program of China(2022YFB4101800)National Natural Science Foundation of China(22278077,22108040)+2 种基金Key Program of Qingyuan Innovation Laboratory(00221004)Research Program of Qingyuan Innovation Laboratory(00523006)Natural Science Foundation of Fujian Province(2022J02019)。
文摘Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.
基金sponsored by the National Natural Science Foundation of China (Nos. 22208140 and 22078145)。
文摘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.
