In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with l...In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.展开更多
Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-...Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes.Herein,we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide)(Pebax) matrix for efficient separation H_(2)S and CO_(2)from CH_(4).Notably,the optimal permeability of H_(2)S reaches up to 4310 Barrer (40C,0.50 bar) in Pebax/ECPIL membranes,along with H_(2)S/CH_(4)and (H_(2)StCO_(2))/CH_(4)selectivity of 97.7 and 112.3,respectively.These values are increased by 1125%,160.8%and 145.9%compared to those in neat Pebax membrane.Additionally,the solubility and diffusion coefficients of the gases were measured,demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H_(2)S and CO_(2),thus elevating the permeability and permselectivity.By using quantum chemical calculations and FT-IR spectroscopy,the highly reversible multi-site hydrogen bonding interaction between ECPILs and H_(2)S was revealed,which is responsible for the fast permeation of H_(2)S and good selectivity.Furthermore,H_(2)S/CO_(2)/CH_(4)(3/3/94 mol/mol) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h.Overall,this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H_(2)S and CO_(2),but may also provide a novel insight into the design of membrane materials for natural gas upgrading.展开更多
A series of multi-hydroxyl bis-(quaternary ammonium)ionic liquids(Ils1‒7)was prepared as bifunctional catalysts for the chemical fixation of CO_(2).All these ionic liquid compounds were efficient for the catalytic syn...A series of multi-hydroxyl bis-(quaternary ammonium)ionic liquids(Ils1‒7)was prepared as bifunctional catalysts for the chemical fixation of CO_(2).All these ionic liquid compounds were efficient for the catalytic synthesis of cyclic carbonates and oxazolidinones via the cycloaddition reactions between CO_(2) and epoxides or aziridines with excellent yield and high selectivity in the absence of co-catalyst,metal and solvent.Due to the synergistic effects of hydroxyl groups and halogen anion,the cycloaddition reactions proceeded smoothly either at atmospheric pressure or room temperature.The selectivity for substituted oxazolidinones at 5-and 4-positions can be tuned via changing the reaction conditions.Finally,possible mechanisms including the activation of both CO_(2) and epoxide or aziridines were proposed based on the literatures and experimental results.展开更多
The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel ap...The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time,with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery.Remarkably,the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate(C_(4)mim-Fe Cl_(4))demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins.This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.展开更多
Electrochemical reduction of CO_(2)is a promising approach to convert CO_(2)to high-valued chemicals and fuels.However,developing efficient electrocatalysts featuring desirable activity and selectivity is still a big ...Electrochemical reduction of CO_(2)is a promising approach to convert CO_(2)to high-valued chemicals and fuels.However,developing efficient electrocatalysts featuring desirable activity and selectivity is still a big challenge.In this work,a strategy of introducing functionalized molecules with desirable CO_(2)affinity to regulate Ag catalyst for promoting electrochemical reduction of CO_(2)was proposed.Specifically,3-mercapto-1,2,4-triazole was introduced onto the Ag nanoparticle(Ag-m-Triz)for the first time to achieve selectively converting CO_(2)to carbon monoxide(CO).This Ag-m-Triz exhibits excellent performance for CO_(2)reduction with a high CO Faradaic efficiency(FECO)of 99.2%and CO partial current density of 85.0 mA cm^(-2)at-2.3 V vs.Ag/Ag^(+) in H-cell when combined with the ionic liquid-based electrolyte,30 wt%1-butyl-3-methylimidazolium hexafluorophosphate([Bmim][PF6])-65 wt%acetonitrile(AcN)-5 wt%H2O,which is 2.5-fold higher than the current density in Ag-powder under the same condition.Mechanism studies confirm that the significantly improved performance of Ag-m-Triz originates from(i)the stronger adsorption ability of CO_(2)molecule and(ii)the weaker binding energy to form the COOH*intermediate on the surface of Ag-m-Triz compared with the Ag-powder catalyst,which boosts the conversion of CO_(2)to CO.This research provides a facile way to regulate electrocatalysts for efficient CO_(2)reduction by introducing functionalized molecules.展开更多
A novel composite material,Poly(IL-AA)@MIL-101(Cr),combining metal-organic framework,polymeric ionic liquid and acrylic acid,was synthesized for the selective and efficient adsorption of rare earths europium(Ⅲ)(Eu3+)...A novel composite material,Poly(IL-AA)@MIL-101(Cr),combining metal-organic framework,polymeric ionic liquid and acrylic acid,was synthesized for the selective and efficient adsorption of rare earths europium(Ⅲ)(Eu3+).Characterization of the materials was carried out using techniques such as X-ray diffraction(XRD),Fourier transform infrared(FTIR),scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS),thermogravimetric analysis(TGA)and Brunauer-Emmett-Teller(BET).The results demonstrate successful incorporation of the polymeric ionic liquid onto the material surface while preserving the crystal structure and mo rphology of MIL-101(Cr).Adsorption experiments were conducted to explore parameters including equilibrium pH,initial Eu3+concentration,and duration,with comprehensive analyses of adsorption kinetics,isotherms,and mechanisms.Findings reveal that Poly(IL1-AA)@MIL-101(Cr),Poly(IL3-AA)@MIL-101(Cr),and Poly(IL5-AA)@MIL-101(Cr)achieve adsorption equilibrium for Eu3+at approximately 9 h with an equilibrium pH of 6.2.The adso rption of Eu^(3+)predominantly follows a pseudo-second-order kinetic model and Langmuir isotherm adsorption model.Moreover,the prepared composite material exhibits superior adsorption selectivity for Eu^(3+)over other metal ions in the mixture(K^(+),Mg^(2+),Ni^(2+),Co^(2+),Zn^(2+),La^(3+),and Nd^(3+)).Even after five adsorption-desorption cycles,the composite material maintains satis factory adsorption performance.展开更多
The composite membrane of microcrystalline cellulose(MCC)with polyvinyl alcohol(PVA)was effectively synthesized using ionic liquids(ILs)as the solvent and dimethyl sulfone(DMSO)as the co-solvent through the phase conv...The composite membrane of microcrystalline cellulose(MCC)with polyvinyl alcohol(PVA)was effectively synthesized using ionic liquids(ILs)as the solvent and dimethyl sulfone(DMSO)as the co-solvent through the phase conversion method.The effects of IL structure and the IL/DMSO mass ratio on the solubility of MCC were investigated.The findings indicated that the composite solvent functioned as a non-derivative solvent for MCC dissolution.The inclusion of DMSO decreased the viscosity of ILs and enhanced the rate of MCC dissolution.The solubility of MCC reached 14.5%(mass)when the mass ratio of[Bmim]Cl to DMSO was 1:1.The fabricated MCC membrane exhibited a smooth surface and a dense structure.PVA@MCC demonstrated exceptional mechanical properties and a uniform structure at a mass ratio of 2:1,with an elongation at break of 76%and a tensile strength of 14.6 MPa.The effects of antibacterial agents on the morphology,transmittance,mechanical properties,and antibacterial efficiency of PVA@MCC were investigated.The findings revealed that PVA@MCC fortified with clove oil showcased a flat and smooth surface,devoid of stratification or aggregation,and demonstrated superior mechanical properties compared to its counterparts with chitosan and ZnO additions.The elongation at break of PVA@MCC with clove oil increased to 137.6%,while its tensile strength decreased to 10.4 MPa.PVA@MCC with clove oil exhibited an antibacterial efficiency exceeding 68%against Escherichia coli,Staphylococcus aureus,and Pseudomonas aeruginosa,thereby extending the shelf life of cherry tomatoes by an additional four days at ambient temperature.展开更多
The recovery of ionic liquids(ILs)has attracted growing attention as an indispensable process in“green”industrial applications.Forward osmosis(FO)has proven to be a sustainable method for concentrating the very dilu...The recovery of ionic liquids(ILs)has attracted growing attention as an indispensable process in“green”industrial applications.Forward osmosis(FO)has proven to be a sustainable method for concentrating the very dilute aqueous solutions of ILs at ambient temperature,in which semi-permeable membranes play a vital role in determining the recovery efficiency.Herein,we use interfacial polymerization method to prepare thin-film composite membranes consisting of polyamide skin layer and electrospun nanofibrous substrate with tunable water permeability and IL selectivity for osmotic enrichment of imidazolium ILs from their dilute aqueous solutions through FO process.The resulting FO membrane shows a compact polyamide layer with a thickness of 30-200 nm,guranteeing a high selectivity to ILs and water.Meanwhile,the nanofibrous substrate with large and interconnect pores as well as low tortuosity,providing mechanical and permeable support for the composite membranes.IL structure influences the osmotic pressure difference as well as the interactions with polyamide layer of the membrane and thus determines the whole concentration process.First,the alkyl chain growth augments the osmosis pressure difference between the ILs solution and draw solution,resulting in an enhancement in driving force of water osmosis and IL enrichment.Moreover,alkyl length aggravates external concentration polarization caused by the enhanced adsorption of ILs onto the skin layer via electrostatic and alkyl-πinteractions.Meanwhile,such adsorbed ILs further enhance the IL retention but decrease the reverse salt diffusion.Therefore,imidazolium ILs with varied alkyl lengths are ultimately enriched with a 100-fold increase in concentration from their dilute aqueous solutions with high IL/NaCl rejection and low IL loss.Remarkably,the final concentration of IL with longest alkyl length reaches the highest(6.4 mol·L^(-1)).This work provides the insights in respect to material preparation and process amelioration for IL recovery with high scalability at mild conditions.展开更多
Flammable ionic liquids exhibit high conductivity and a broad electrochemical window,enabling the generation of combustible gases for combustion via electrochemical decomposition and thermal decomposition.This charact...Flammable ionic liquids exhibit high conductivity and a broad electrochemical window,enabling the generation of combustible gases for combustion via electrochemical decomposition and thermal decomposition.This characteristic holds significant implications in the realm of novel satellite propulsion.Introducing a fraction of the electrical energy into energetic ionic liquid fuels,the thermal decomposition process is facilitated by reducing the apparent activation energy required,and electrical energy can trigger the electrochemical decomposition of ionic liquids,presenting a promising approach to enhance combustion efficiency and energy release.This study applied an external voltage during the thermal decomposition of 1-ethyl-3-methylimidazole nitrate([EMIm]NO_(3)),revealing the effective alteration of the activation energy of[EMIm]NO_(3).The pyrolysis,electrochemical decomposition,and electron assisted enhancement products were identified through Thermogravimetry-Differential scanning calorimetry-Fourier transform infrared-Mass spectrometry(TG-DSC-FTIR-MS)and gas chromatography(GC)analyses,elucidating the degradation mechanism of[EMIm]NO_(3).Furthermore,an external voltage was introduced during the combustion of[EMIm]NO_(3),demonstrating the impact of voltage on the combustion process.展开更多
Conversion and capture of carbon pollutants based on carbon dioxide to valuable green oil-field chemicals are target all over the world for controlling the global warming.The present article used new room temperature ...Conversion and capture of carbon pollutants based on carbon dioxide to valuable green oil-field chemicals are target all over the world for controlling the global warming.The present article used new room temperature amphiphilic imidazolium ionic liquids with superior surface activity in the aqueous solutions to convert carbon dioxide gas to superior amphiphilic calcium carbonate nanoparticles.In this respect,tetra-cationic ionic liquids 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate and 2-(4-hexyldimethylamino)phenyl)-1,3-bis(3-hexcyldimethylammnonio)propyl)bromide-1 H-imidazol-3-ium acetate were prepared.Their chemical structures,thermal as well as their carbon dioxide absorption/desorption characteristicswere evaluated.Theywere used as solvent and capping agent to synthesize calcium carbonate nanoparticles with controlled crystalline lattice,sizes,thermal properties and spherical surface morphologies.The prepared calcium carbonate nanoparticles were used as additives for the commercial water based drilling mud to improve their filter lose and rheology.The data confirm that the lower concentrations of 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate achieved lower seawater filter lose and improved viscosities.展开更多
Carbon dioxide(CO_(2))is the predominant greenhouse gas in the Earth’s atmosphere and plays a crucial role in global warming.Given the inherent limitations of monoethanolamine absorbents in current commercial large-s...Carbon dioxide(CO_(2))is the predominant greenhouse gas in the Earth’s atmosphere and plays a crucial role in global warming.Given the inherent limitations of monoethanolamine absorbents in current commercial large-scale CO_(2)capture applications,amino acid ionic liquids(AAILs)have garnered extensive interest in this field due to their adjustable structure,low volatility,high thermal stability,and significant absorption capacity.However,the number of comprehensive reviews recently published on the CO_(2)absorption by AAILs remains limited.In addition,researchers have differing opinions on the AAILs/CO_(2)reaction mechanisms.Therefore,this review provides a thorough overview of the reaction mechanisms and structure-activity relationships associated with AAILs for CO_(2)capture.Moreover,it outlines the research advancements in pure AAILs and their mixtures,including aqueous AAILs and AAIL-organic solvent mixtures.The effects of varying ionic structures and additives on the absorption properties of AAILs are examined in detail.In conclusion,although AAILs exhibit high CO_(2)absorption loading and possess numerous appealing characteristics,further research is essential to comprehensively evaluate their viability for large-scale CO_(2)capture from flue gas.展开更多
Aluminum was electrodeposited with constant current on AZ31 magnesium alloy pretreated under optimized conditions from trimethyl-phenyl-ammonium chloride and anhydrous aluminum chloride （TMPAC-AlCl3） quaternary ammo...Aluminum was electrodeposited with constant current on AZ31 magnesium alloy pretreated under optimized conditions from trimethyl-phenyl-ammonium chloride and anhydrous aluminum chloride （TMPAC-AlCl3） quaternary ammonium room temperature ionic liquids with benzene as a co-solvent. The corrosion resistance of the as-deposited Al layers was evaluated in 3.5% NaCl solution by the electrochemical technologies. The Al depositions were characterized by scanning electron microscopy equipped with energy dispersion X-ray. The results show that the microstructures of the Al depositions have spherical equiaxed grains obtained at a high current density, and bulk grains at a low current density. The Al deposition obtained at 12.3 mA/cm2 has a smooth and compact surface. The electrochemical measurements indicate that the thicker Al deposition can more effectively protect the Mg substrate. The Al deposition with bulk grains hardly protects the AZ31 Mg substrate from corrosion owing to its porosity.展开更多
It is difficult to directly electroplate Al on Mg alloys. The effects of pretreatment parameters on the corrosion resistance of films obtained on AZ31 Mg alloy surface were studied by using potentiodynamic polarizatio...It is difficult to directly electroplate Al on Mg alloys. The effects of pretreatment parameters on the corrosion resistance of films obtained on AZ31 Mg alloy surface were studied by using potentiodynamic polarization curves, to produce a compact interfacial layer as zinc-immersion deposition. After the substrate was pretreated under optimized conditions, aluminum was electrodeposited on AZ31 from TMPAC-AlCl3 room temperature ionic liquids. The depositions were characterized by scanning electron microscope equipped with energy dispersion X-ray. The results show that the traditional pretreatment of Mg alloys was successfully used for the Al-electroplating process from TMPAC-AlCl3 ionic liquids. The entire procedure includes alkaline cleaning, chemical pickling, surface activation （400 mL/L HF acid, 10 min）, zinc-immersion （20 min） and anhydrous treatment. A relatively compact zinc-immersion film was prepared on the substrate surface. A silvery-colored satin aluminum deposition was obtained on AZ31 from TMPAC-AlCl3 using direct current plating.展开更多
Quantum mechanics and molecular dynamics are used to simulate guanidinium ionic liquids. Results show that the stronger interaction exists between guanidine cation and chlorine anion with interaction energy about 109....Quantum mechanics and molecular dynamics are used to simulate guanidinium ionic liquids. Results show that the stronger interaction exists between guanidine cation and chlorine anion with interaction energy about 109.216 kcal/mol. There are two types of spatial distribution for the title system： middle and top. Middle mode is a more stable conformation according to energy and geometric distribution. It is also verified by radial distribution function. The continuous increase of carbon dioxide （CO2） does not affect the structure of ionic liquids, but CO2 molecules are always captured by the cavity of ionic liquids.展开更多
Binary mixtures of 1,3-dialkylimidazolium based ionic liquids （ILs） and water were selected as solvent systems to investigate the solute-solvent and solvent-solvent interactions on the preferential solvation of solv...Binary mixtures of 1,3-dialkylimidazolium based ionic liquids （ILs） and water were selected as solvent systems to investigate the solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators at 25 ℃. Empirical solvatochromic pa- rameters, dipolarity/polarizability （π^＊）, hydrogen-bond donor acidity （α）, hydrogen-bond acceptor basicity （β）, and Reichardt＇s polarity parameters （ET^N） were measured from the ultraviolet-visible spectral shifts of 4-nitroaniline, 4-nitroanisole, and Reichardt＇s dye. The solvent properties of the IL-water mixtures were found to be influenced by IL type and IL mole fraction （XIL）. All these studied systems showed the non-ideal behavior. The max- imum deviation to ideality for the solvatochromic parameters can be obtained in the XIL range from 0.i to 0.3. For most of the binary mixtures, the π^＊ values showed the synergistic effects instead of the ETN, α and β values. The observed synergy extent was dependent on the studied systems, such as the dye indicator and IL type. A preferential solvation model was utilized to gather information on the molecular interactions in the mixtures. The dye indicator was preferentially solvated on the following trend： IL〉IL-water complex〉water.展开更多
Due to the large number of ionic liquids （ILs） and their potential environmental risk, assessing the toxicity of ILs by ecotoxicological experiment only is insufficient. Quantitative structure- activity relationship...Due to the large number of ionic liquids （ILs） and their potential environmental risk, assessing the toxicity of ILs by ecotoxicological experiment only is insufficient. Quantitative structure- activity relationship （QSAR） has been proven to be a quick and effective method to estimate the viscosity, melting points, and even toxicity of ILs. In this work, the LC50 values of 30 imidazolium-based ILs were determined with Caenorhabditis elegans as a model animal. Four suitable molecular descriptors were selected on the basis of genetic function approximation algorithm to construct a QSAR model with an R^2 value of 0.938. The predicted lgLC50 in this work are in agreement with the experimental values, indicating that the model has good stability and predictive ability. Our study provides a valuable model to predict the potential toxicity of ILs with different sub-structures to the environment and human health.展开更多
Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of ...Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.展开更多
A novel bifunctional task-specific ionic liquid(TSIL),i.e.[trialkylmethylammonium][sec-nonylphenoxy acetate]([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin,and the prepared solvent impreganated...A novel bifunctional task-specific ionic liquid(TSIL),i.e.[trialkylmethylammonium][sec-nonylphenoxy acetate]([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin,and the prepared solvent impreganated resin(SIR) was studied for rare earth(RE) separation.Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100].Adsorption kinetics,adsorption isotherm,separation and desorption of the SIR were also stu...展开更多
文摘In this work,we proposed a strategy for the hydrolysis of native corn starch after the treatment of corn starch in an ionic liquid aqueous solution,and it is an awfully“green”and simple means to obtain starch with low molecular weight and amorphous state.X-ray diffraction results revealed that the natural starch crystalline region was largely disrupted by ionic liquid owing to the broken intermolecular and intramolecular hydrogen bonds.After hydrolysis,the morphology of starch changed from particles of native corn starch into little pieces,and their molecular weight could be effectively regulated during the hydrolysis process,and also the hydrolyzed starch samples exhibited decreased thermal stability with the extension of hydrolysis time.This work would counsel as a powerful tool for the development of native starch in realistic applications.
基金sponsored by the National Natural Science Foundation of China (Nos. 22308145, 22208140, 22178159, 22078145)Natural Science Foundation of Jiangsu Province (BK20230791)Postgraduate Research Innovation Program of Jiangsu Province (KYCX24_0165)。
文摘Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes.Herein,we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide)(Pebax) matrix for efficient separation H_(2)S and CO_(2)from CH_(4).Notably,the optimal permeability of H_(2)S reaches up to 4310 Barrer (40C,0.50 bar) in Pebax/ECPIL membranes,along with H_(2)S/CH_(4)and (H_(2)StCO_(2))/CH_(4)selectivity of 97.7 and 112.3,respectively.These values are increased by 1125%,160.8%and 145.9%compared to those in neat Pebax membrane.Additionally,the solubility and diffusion coefficients of the gases were measured,demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H_(2)S and CO_(2),thus elevating the permeability and permselectivity.By using quantum chemical calculations and FT-IR spectroscopy,the highly reversible multi-site hydrogen bonding interaction between ECPILs and H_(2)S was revealed,which is responsible for the fast permeation of H_(2)S and good selectivity.Furthermore,H_(2)S/CO_(2)/CH_(4)(3/3/94 mol/mol) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h.Overall,this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H_(2)S and CO_(2),but may also provide a novel insight into the design of membrane materials for natural gas upgrading.
文摘A series of multi-hydroxyl bis-(quaternary ammonium)ionic liquids(Ils1‒7)was prepared as bifunctional catalysts for the chemical fixation of CO_(2).All these ionic liquid compounds were efficient for the catalytic synthesis of cyclic carbonates and oxazolidinones via the cycloaddition reactions between CO_(2) and epoxides or aziridines with excellent yield and high selectivity in the absence of co-catalyst,metal and solvent.Due to the synergistic effects of hydroxyl groups and halogen anion,the cycloaddition reactions proceeded smoothly either at atmospheric pressure or room temperature.The selectivity for substituted oxazolidinones at 5-and 4-positions can be tuned via changing the reaction conditions.Finally,possible mechanisms including the activation of both CO_(2) and epoxide or aziridines were proposed based on the literatures and experimental results.
基金financial support from the National Natural Science Foundation of China(Nos.22071222,22171249)the Natural Science Foundation of Henan Province(Nos.232300421363,242300420526)+2 种基金Key Research Projects of Universities in Henan Province(No.23A180010)Science&Technology Innovation Talents in Universities of Henan Province(No.23HASTIT003)Science and Technology Research and Development Plan Joint Fund of Henan Province(No.242301420006)。
文摘The photoinduced ligand-to-metal charge transfer(LMCT)process has been extensively investigated,however,the recovery of photocatalysts has remained a persistent challenge in the field.In light of this issue,a novel approach involving the development of iron-based ionic liquids as photocatalysts has been pursued for the first time,with the goal of simultaneously facilitating the LMCT process and addressing the issue of photocatalyst recovery.Remarkably,the iron-based ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate(C_(4)mim-Fe Cl_(4))demonstrates exceptional recyclability and stability for the photocatalytic hydroacylation of olefins.This study will pave the way for new approaches to photocatalytic organic synthesis using ionic liquids as recyclable photocatalysts.
基金supported by the Swedish Energy Agency(P47500-1)the National Key R&D Program of China(2020YFA0710200)+2 种基金the National Natural Science Foundation of China(22378401 and U22A20416)the financial support from STINT(CH2019-8287)support from the European Union and Swedish Energy Agency(P2020-90066).
文摘Electrochemical reduction of CO_(2)is a promising approach to convert CO_(2)to high-valued chemicals and fuels.However,developing efficient electrocatalysts featuring desirable activity and selectivity is still a big challenge.In this work,a strategy of introducing functionalized molecules with desirable CO_(2)affinity to regulate Ag catalyst for promoting electrochemical reduction of CO_(2)was proposed.Specifically,3-mercapto-1,2,4-triazole was introduced onto the Ag nanoparticle(Ag-m-Triz)for the first time to achieve selectively converting CO_(2)to carbon monoxide(CO).This Ag-m-Triz exhibits excellent performance for CO_(2)reduction with a high CO Faradaic efficiency(FECO)of 99.2%and CO partial current density of 85.0 mA cm^(-2)at-2.3 V vs.Ag/Ag^(+) in H-cell when combined with the ionic liquid-based electrolyte,30 wt%1-butyl-3-methylimidazolium hexafluorophosphate([Bmim][PF6])-65 wt%acetonitrile(AcN)-5 wt%H2O,which is 2.5-fold higher than the current density in Ag-powder under the same condition.Mechanism studies confirm that the significantly improved performance of Ag-m-Triz originates from(i)the stronger adsorption ability of CO_(2)molecule and(ii)the weaker binding energy to form the COOH*intermediate on the surface of Ag-m-Triz compared with the Ag-powder catalyst,which boosts the conversion of CO_(2)to CO.This research provides a facile way to regulate electrocatalysts for efficient CO_(2)reduction by introducing functionalized molecules.
基金Project supported by the State Key Laboratory of Geohazard Prevention and Geoenvironment Protection(SKLGP2020Z003)。
文摘A novel composite material,Poly(IL-AA)@MIL-101(Cr),combining metal-organic framework,polymeric ionic liquid and acrylic acid,was synthesized for the selective and efficient adsorption of rare earths europium(Ⅲ)(Eu3+).Characterization of the materials was carried out using techniques such as X-ray diffraction(XRD),Fourier transform infrared(FTIR),scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS),thermogravimetric analysis(TGA)and Brunauer-Emmett-Teller(BET).The results demonstrate successful incorporation of the polymeric ionic liquid onto the material surface while preserving the crystal structure and mo rphology of MIL-101(Cr).Adsorption experiments were conducted to explore parameters including equilibrium pH,initial Eu3+concentration,and duration,with comprehensive analyses of adsorption kinetics,isotherms,and mechanisms.Findings reveal that Poly(IL1-AA)@MIL-101(Cr),Poly(IL3-AA)@MIL-101(Cr),and Poly(IL5-AA)@MIL-101(Cr)achieve adsorption equilibrium for Eu3+at approximately 9 h with an equilibrium pH of 6.2.The adso rption of Eu^(3+)predominantly follows a pseudo-second-order kinetic model and Langmuir isotherm adsorption model.Moreover,the prepared composite material exhibits superior adsorption selectivity for Eu^(3+)over other metal ions in the mixture(K^(+),Mg^(2+),Ni^(2+),Co^(2+),Zn^(2+),La^(3+),and Nd^(3+)).Even after five adsorption-desorption cycles,the composite material maintains satis factory adsorption performance.
基金financial support of the Scientific Research Funds of Huaqiao University(605-50Y17073),Xiamen,China.
文摘The composite membrane of microcrystalline cellulose(MCC)with polyvinyl alcohol(PVA)was effectively synthesized using ionic liquids(ILs)as the solvent and dimethyl sulfone(DMSO)as the co-solvent through the phase conversion method.The effects of IL structure and the IL/DMSO mass ratio on the solubility of MCC were investigated.The findings indicated that the composite solvent functioned as a non-derivative solvent for MCC dissolution.The inclusion of DMSO decreased the viscosity of ILs and enhanced the rate of MCC dissolution.The solubility of MCC reached 14.5%(mass)when the mass ratio of[Bmim]Cl to DMSO was 1:1.The fabricated MCC membrane exhibited a smooth surface and a dense structure.PVA@MCC demonstrated exceptional mechanical properties and a uniform structure at a mass ratio of 2:1,with an elongation at break of 76%and a tensile strength of 14.6 MPa.The effects of antibacterial agents on the morphology,transmittance,mechanical properties,and antibacterial efficiency of PVA@MCC were investigated.The findings revealed that PVA@MCC fortified with clove oil showcased a flat and smooth surface,devoid of stratification or aggregation,and demonstrated superior mechanical properties compared to its counterparts with chitosan and ZnO additions.The elongation at break of PVA@MCC with clove oil increased to 137.6%,while its tensile strength decreased to 10.4 MPa.PVA@MCC with clove oil exhibited an antibacterial efficiency exceeding 68%against Escherichia coli,Staphylococcus aureus,and Pseudomonas aeruginosa,thereby extending the shelf life of cherry tomatoes by an additional four days at ambient temperature.
基金supported by the National Natural Science Foundation of China(No.52173095)the MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Zhejiang University(No.2023MSF05)。
文摘The recovery of ionic liquids(ILs)has attracted growing attention as an indispensable process in“green”industrial applications.Forward osmosis(FO)has proven to be a sustainable method for concentrating the very dilute aqueous solutions of ILs at ambient temperature,in which semi-permeable membranes play a vital role in determining the recovery efficiency.Herein,we use interfacial polymerization method to prepare thin-film composite membranes consisting of polyamide skin layer and electrospun nanofibrous substrate with tunable water permeability and IL selectivity for osmotic enrichment of imidazolium ILs from their dilute aqueous solutions through FO process.The resulting FO membrane shows a compact polyamide layer with a thickness of 30-200 nm,guranteeing a high selectivity to ILs and water.Meanwhile,the nanofibrous substrate with large and interconnect pores as well as low tortuosity,providing mechanical and permeable support for the composite membranes.IL structure influences the osmotic pressure difference as well as the interactions with polyamide layer of the membrane and thus determines the whole concentration process.First,the alkyl chain growth augments the osmosis pressure difference between the ILs solution and draw solution,resulting in an enhancement in driving force of water osmosis and IL enrichment.Moreover,alkyl length aggravates external concentration polarization caused by the enhanced adsorption of ILs onto the skin layer via electrostatic and alkyl-πinteractions.Meanwhile,such adsorbed ILs further enhance the IL retention but decrease the reverse salt diffusion.Therefore,imidazolium ILs with varied alkyl lengths are ultimately enriched with a 100-fold increase in concentration from their dilute aqueous solutions with high IL/NaCl rejection and low IL loss.Remarkably,the final concentration of IL with longest alkyl length reaches the highest(6.4 mol·L^(-1)).This work provides the insights in respect to material preparation and process amelioration for IL recovery with high scalability at mild conditions.
基金supported by the National Natural Science Foundation of China(Grant No.52206165)。
文摘Flammable ionic liquids exhibit high conductivity and a broad electrochemical window,enabling the generation of combustible gases for combustion via electrochemical decomposition and thermal decomposition.This characteristic holds significant implications in the realm of novel satellite propulsion.Introducing a fraction of the electrical energy into energetic ionic liquid fuels,the thermal decomposition process is facilitated by reducing the apparent activation energy required,and electrical energy can trigger the electrochemical decomposition of ionic liquids,presenting a promising approach to enhance combustion efficiency and energy release.This study applied an external voltage during the thermal decomposition of 1-ethyl-3-methylimidazole nitrate([EMIm]NO_(3)),revealing the effective alteration of the activation energy of[EMIm]NO_(3).The pyrolysis,electrochemical decomposition,and electron assisted enhancement products were identified through Thermogravimetry-Differential scanning calorimetry-Fourier transform infrared-Mass spectrometry(TG-DSC-FTIR-MS)and gas chromatography(GC)analyses,elucidating the degradation mechanism of[EMIm]NO_(3).Furthermore,an external voltage was introduced during the combustion of[EMIm]NO_(3),demonstrating the impact of voltage on the combustion process.
基金supported by Science,Technology&Innovation Funding Authority(STDF)under grant(No.47062).
文摘Conversion and capture of carbon pollutants based on carbon dioxide to valuable green oil-field chemicals are target all over the world for controlling the global warming.The present article used new room temperature amphiphilic imidazolium ionic liquids with superior surface activity in the aqueous solutions to convert carbon dioxide gas to superior amphiphilic calcium carbonate nanoparticles.In this respect,tetra-cationic ionic liquids 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate and 2-(4-hexyldimethylamino)phenyl)-1,3-bis(3-hexcyldimethylammnonio)propyl)bromide-1 H-imidazol-3-ium acetate were prepared.Their chemical structures,thermal as well as their carbon dioxide absorption/desorption characteristicswere evaluated.Theywere used as solvent and capping agent to synthesize calcium carbonate nanoparticles with controlled crystalline lattice,sizes,thermal properties and spherical surface morphologies.The prepared calcium carbonate nanoparticles were used as additives for the commercial water based drilling mud to improve their filter lose and rheology.The data confirm that the lower concentrations of 2-(4-dodecyldimethylamino)phenyl)-1,3-bis(3-dodecyldimethylammnonio)propyl)bromide-1-H-imidazol-3-ium acetate achieved lower seawater filter lose and improved viscosities.
基金supported by the Natural Science Foundation of Shanghai(Grant No.24ZR1426200)the support from the Key Program of the National Natural Science Foundation of China(Grant No.52236004)。
文摘Carbon dioxide(CO_(2))is the predominant greenhouse gas in the Earth’s atmosphere and plays a crucial role in global warming.Given the inherent limitations of monoethanolamine absorbents in current commercial large-scale CO_(2)capture applications,amino acid ionic liquids(AAILs)have garnered extensive interest in this field due to their adjustable structure,low volatility,high thermal stability,and significant absorption capacity.However,the number of comprehensive reviews recently published on the CO_(2)absorption by AAILs remains limited.In addition,researchers have differing opinions on the AAILs/CO_(2)reaction mechanisms.Therefore,this review provides a thorough overview of the reaction mechanisms and structure-activity relationships associated with AAILs for CO_(2)capture.Moreover,it outlines the research advancements in pure AAILs and their mixtures,including aqueous AAILs and AAIL-organic solvent mixtures.The effects of varying ionic structures and additives on the absorption properties of AAILs are examined in detail.In conclusion,although AAILs exhibit high CO_(2)absorption loading and possess numerous appealing characteristics,further research is essential to comprehensively evaluate their viability for large-scale CO_(2)capture from flue gas.
文摘Aluminum was electrodeposited with constant current on AZ31 magnesium alloy pretreated under optimized conditions from trimethyl-phenyl-ammonium chloride and anhydrous aluminum chloride （TMPAC-AlCl3） quaternary ammonium room temperature ionic liquids with benzene as a co-solvent. The corrosion resistance of the as-deposited Al layers was evaluated in 3.5% NaCl solution by the electrochemical technologies. The Al depositions were characterized by scanning electron microscopy equipped with energy dispersion X-ray. The results show that the microstructures of the Al depositions have spherical equiaxed grains obtained at a high current density, and bulk grains at a low current density. The Al deposition obtained at 12.3 mA/cm2 has a smooth and compact surface. The electrochemical measurements indicate that the thicker Al deposition can more effectively protect the Mg substrate. The Al deposition with bulk grains hardly protects the AZ31 Mg substrate from corrosion owing to its porosity.
文摘It is difficult to directly electroplate Al on Mg alloys. The effects of pretreatment parameters on the corrosion resistance of films obtained on AZ31 Mg alloy surface were studied by using potentiodynamic polarization curves, to produce a compact interfacial layer as zinc-immersion deposition. After the substrate was pretreated under optimized conditions, aluminum was electrodeposited on AZ31 from TMPAC-AlCl3 room temperature ionic liquids. The depositions were characterized by scanning electron microscope equipped with energy dispersion X-ray. The results show that the traditional pretreatment of Mg alloys was successfully used for the Al-electroplating process from TMPAC-AlCl3 ionic liquids. The entire procedure includes alkaline cleaning, chemical pickling, surface activation （400 mL/L HF acid, 10 min）, zinc-immersion （20 min） and anhydrous treatment. A relatively compact zinc-immersion film was prepared on the substrate surface. A silvery-colored satin aluminum deposition was obtained on AZ31 from TMPAC-AlCl3 using direct current plating.
基金ACKNOWLEDGMENTS This work was supported by the Open Project Program of Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, Hunan University of Science and Technology, China （No.E21104）, the National Natural Science Foundation of China （No.21201062 and No.21172066）, and the International Cooperation Project （No.2013DFG60060）.
文摘Quantum mechanics and molecular dynamics are used to simulate guanidinium ionic liquids. Results show that the stronger interaction exists between guanidine cation and chlorine anion with interaction energy about 109.216 kcal/mol. There are two types of spatial distribution for the title system： middle and top. Middle mode is a more stable conformation according to energy and geometric distribution. It is also verified by radial distribution function. The continuous increase of carbon dioxide （CO2） does not affect the structure of ionic liquids, but CO2 molecules are always captured by the cavity of ionic liquids.
文摘Binary mixtures of 1,3-dialkylimidazolium based ionic liquids （ILs） and water were selected as solvent systems to investigate the solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators at 25 ℃. Empirical solvatochromic pa- rameters, dipolarity/polarizability （π^＊）, hydrogen-bond donor acidity （α）, hydrogen-bond acceptor basicity （β）, and Reichardt＇s polarity parameters （ET^N） were measured from the ultraviolet-visible spectral shifts of 4-nitroaniline, 4-nitroanisole, and Reichardt＇s dye. The solvent properties of the IL-water mixtures were found to be influenced by IL type and IL mole fraction （XIL）. All these studied systems showed the non-ideal behavior. The max- imum deviation to ideality for the solvatochromic parameters can be obtained in the XIL range from 0.i to 0.3. For most of the binary mixtures, the π^＊ values showed the synergistic effects instead of the ETN, α and β values. The observed synergy extent was dependent on the studied systems, such as the dye indicator and IL type. A preferential solvation model was utilized to gather information on the molecular interactions in the mixtures. The dye indicator was preferentially solvated on the following trend： IL〉IL-water complex〉water.
基金This work was supported by the National Natural Science Foundation of China （No.21477121）, and the Fundamental Research Funds for the Central Universities for the support of this work. The numerical calculations were performed on the super computing system in the Supercomputing Center at the University of Science and Technology of China.
文摘Due to the large number of ionic liquids （ILs） and their potential environmental risk, assessing the toxicity of ILs by ecotoxicological experiment only is insufficient. Quantitative structure- activity relationship （QSAR） has been proven to be a quick and effective method to estimate the viscosity, melting points, and even toxicity of ILs. In this work, the LC50 values of 30 imidazolium-based ILs were determined with Caenorhabditis elegans as a model animal. Four suitable molecular descriptors were selected on the basis of genetic function approximation algorithm to construct a QSAR model with an R^2 value of 0.938. The predicted lgLC50 in this work are in agreement with the experimental values, indicating that the model has good stability and predictive ability. Our study provides a valuable model to predict the potential toxicity of ILs with different sub-structures to the environment and human health.
基金Supported by the National Natural Science Foundation of China(No.21725603)Zhejiang Provincial Natural Science Foundation of China(LZ18B060001)the National Program for Support of Top-notch Young Professionals(H.X.)
文摘Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.
基金supported by ‘Hundreds Talents Program’from Chinese Academy of Sciences, National Natural Science Foundation of China (50574080, 20901073)National Key Technology R&D Program of China (2006BAC02A10)Distinguished Young Scholar Foundation of Jilin Province (20060114)
文摘A novel bifunctional task-specific ionic liquid(TSIL),i.e.[trialkylmethylammonium][sec-nonylphenoxy acetate]([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin,and the prepared solvent impreganated resin(SIR) was studied for rare earth(RE) separation.Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100].Adsorption kinetics,adsorption isotherm,separation and desorption of the SIR were also stu...
