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
Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are ineffi...Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.展开更多
Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids were used as promising elec-trolytes in the low-temperature electrodeposition of aluminium.Systematic studies on deposition process have been perf...Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids were used as promising elec-trolytes in the low-temperature electrodeposition of aluminium.Systematic studies on deposition process have been performed by cyclic voltammetry and chronoamperometry.The surface morphology and X-ray diffraction(XRD) patterns of deposits prepared at different experimental conditions were also investigated.It was shown that the nu-cleation density and growth rate of crystallites had a great effect on the structure of aluminium deposited.The crys-tallographic orientation of deposits was mainly influenced by temperature and current density.Smooth,dense and well adherent aluminium coatings were obtained on copper substrates at 10-25 mA?cm?2 and 313.2-353.2 K.More-over,the current efficiency of deposition and purity of aluminium have been significantly improved,demonstrating that the ionic liquids tested have a prospectful potential in electroplating and electrorefining of aluminium.展开更多
A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation proc...A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.展开更多
Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 c...Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.展开更多
α, β-unsaturated esters were often synthesized from aldehydes and esters in the presence of strong organic base that was very sensitive to air and moisture via aldol reaction. Trioxane was very useful C1 resource, h...α, β-unsaturated esters were often synthesized from aldehydes and esters in the presence of strong organic base that was very sensitive to air and moisture via aldol reaction. Trioxane was very useful C1 resource, however, the decomposition of it was always the challenging problem that facing researchers. Herein, a novel synthetic methodology for α, β-unsaturated ester preparation from trioxane and ester with mild catalysis of generated ammonium trifluoromethanesulfonate ionic liquid. The enolization of ester as well as the decomposition of trioxane could proceed easily in the presence of boryl trifluoromethanesulfonate and amine at 20–25℃. Then the enolate and decomposed formaldehyde occurs aldol reaction to form α, β-unsaturated ester. With this strategy, the yield and selectivity of product from various substrates including aliphatic esters,lactones and thioester could reach up to 85.2% and 90.1%.展开更多
In light of the increasing demand for environmental protection and energy conservation,the recovery of highly valuable metals,such as Li,Co,and Ni,from spent lithium-ion batteries(LIBs)has attracted widespread attenti...In light of the increasing demand for environmental protection and energy conservation,the recovery of highly valuable metals,such as Li,Co,and Ni,from spent lithium-ion batteries(LIBs)has attracted widespread attention.Most conventional recycling strategies,however,suffer from a lack of lithium recycling,although they display high efficiency in the recovery of Co and Ni.In this work,we report an efficient extraction process of lithium from the spent LIBs by using a functional imidazolium ionic liquid.The extraction efficiency can be reached to 92.5%after a three-stage extraction,while the extraction efficiency of Ni-Co-Mn is less than 4.0%.The new process shows a high selectivity of lithium ion.FTIR spectroscopy and ultraviolet are utilized to characterize the variations in the functional groups during extraction to reveal that the possible extraction mechanism is cation exchange.The results of this work provide an effective and sustainable strategy of lithium recycling from spent LIBs.展开更多
The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems cont...The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems containing different imidazolium–based ionic liquids(ILs),i.e.MeOH+DMC+1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf2N]),MeOH+DMC+1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf2N]),and MeOH+DMC+1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])were measured at 101.3 kPa.The mole fraction of IL was varied from0.05 to 0.20.The experimental data were correlated with the NRTL and Wilson equations,respectively.The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and[Bmim][Tf2 N]showed a much more excellent performance on the activity coefficient of MeOH.The interaction energies of system components were calculated using Gaussian program,and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.展开更多
A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and...A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and alcohols under mild conditions.The basic strengths of the ionic liquids were evaluated by determination of their Hammett functions,obtained using ultraviolet‐visible spectroscopy,and the relationship between their catalytic activities and basicities was established.The catalytic efficiencies of the ionic liquids were higher than that of the traditional basic catalyst NaOH.This can be attributed to the involvement of a novel reaction mechanism when these ionic liquids are used.A possible electrophilic‐nucleophilic dual activation mechanism was proposed and confirmed using electrospray ionization quadrupole time‐of‐flight mass spectrometry.In addition,the effects of significant reaction parameters such as concentration of catalyst,molar ratio of alcohol to propylene oxide,reaction temperature,and steric hindrance of the alcohol were investigated in detail.展开更多
An ionic liquid(IL)catalyzed solvent-free process was developed for the direct synthesis of chalcone and its derivatives by using substituted acetophenones and benzaldehydes via aldol reaction under mild conditions.A ...An ionic liquid(IL)catalyzed solvent-free process was developed for the direct synthesis of chalcone and its derivatives by using substituted acetophenones and benzaldehydes via aldol reaction under mild conditions.A series of acidic and basic ILs were selected and screened.The influences of cations and reaction conditions on product yield and selectivity were systematically investigated.The[Bmim]OH was identified as the optimal IL,with the highest yield and selectivity reaching up to 96.7% and 100%,respectively.A reaction mechanism-based kinetic model was established and regressed with experimental data,revealing the β-Hydroxylketone dehydrolysis with activation barrier of 37.8 kJ·mol^(-1) was observed as the ratecontrolling step.展开更多
The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to C...The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).展开更多
Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demon...Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.展开更多
The separation of carbon dioxide(CO_(2))is of great importance for environment protection and gas resource purification.The ionic liquids(ILs)-based gas separation membrane provides a new chance for efficient CO_(2)se...The separation of carbon dioxide(CO_(2))is of great importance for environment protection and gas resource purification.The ionic liquids(ILs)-based gas separation membrane provides a new chance for efficient CO_(2)separation,while high permeability and selectivity of membranes is a great challenge.In this study,the influence of two protic ILs with different anion([TMGH][Im]and[TMGH][PhO])on the CO_(2)separation performance of the prepared ILs/Pebax blended membranes were systematically investigated at different temperature.The results showed the CO_(2)permeability exhibits the rising trend for ILs/Pebax blended membranes with the increment of IL content.Especially,the[TMGH][Im]with low viscosity and high CO_(2)absorption capacity leads to the blended membranes showing better CO_(2)permeability and ideal CO_(2)selectivity than that of membranes with[TMGH][PhO]at high IL content.Besides,with operating temperature increasing,the gas permeability of 20%(mass)[TMGH][Im]/Pebax blended membrane increases due to the decreasing viscosity of IL and the rising chain mobility of polymer.Inversely,the gas selectivity shows decreasing trend because CO_(2)absorption capacity obviously decreased at higher temperature.展开更多
Mathematical modeling for nanofiltration of ionic liquids(ILs) solutions could assist to understand transfer mechanism and predict experimental values. In this work, modeling by solution-diffusion model for nanofiltra...Mathematical modeling for nanofiltration of ionic liquids(ILs) solutions could assist to understand transfer mechanism and predict experimental values. In this work, modeling by solution-diffusion model for nanofiltration of long-alkyl-chain ILs aqueous solutions was proposed. Molecular simulations were performed to validate the existence of ion cluster in long-alkyl-chain ILs aqueous solution. Based on the results of simulations, parameters used in the solution-diffusion model were modified, such as concentration of ILs and diameter of ion cluster.The modeling process was developed for three long-alkyl-chain ILs aqueous solutions with different concentrations(1-alkyl-3-methylimidazolium chloride: [C6 mim]Cl, [C8 mim]Cl, [C10 mim]Cl). The calculated values obtained from modified solution-diffusion model could well match the experimental values.展开更多
The confined ionic liquid(IL) in solid polymer composite electrolytes(SCPEs) can improve the performance of lithium metal batteries. However, the impact/role and working mechanism of confined IL in SCPEs remain ambigu...The confined ionic liquid(IL) in solid polymer composite electrolytes(SCPEs) can improve the performance of lithium metal batteries. However, the impact/role and working mechanism of confined IL in SCPEs remain ambiguous. Herein, IL was immobilized on SiO_(2)(SiO_(2)@IL-C) and then used to prepare the confined SCPEs together with LiTFSI and PEO to study the impacts of confined-IL on the properties and performance of electrolytes and reveal the Li+transport mechanism. The results show that, compared to the IL-unconfined SCPE, the IL-confined ones exhibit better performance of electrolytes and cells, such as higher ionic conductivity, higher t+Li, and wider electrochemical windows, as well as more stable cycle performance, due to the increased dissociation degree of lithium salt and enlarged polymer amorphousness. The finite-element/molecular-dynamics simulations suggest that the IL confined on the SiO_(2) provided an additional Li+transport pathway(Li+→ SiO_(2)@IL-C) that can accelerate ion transfer and alleviate lithium dendrites, leading to ultrastable stripping/plating cycling over 1900 h for the Li/SCPEs/Li symmetric cells. This study demonstrates that IL-confinement is an effective strategy for the intelligent approach of high-performance lithium metal batteries.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
Selective oxidation of alkanes to produce highvalue chemicals is an essential strategy and means to realize efficient utilization of resources.In this work,a strategy of lanthanum manganese mixed metal oxides(LMMO)reg...Selective oxidation of alkanes to produce highvalue chemicals is an essential strategy and means to realize efficient utilization of resources.In this work,a strategy of lanthanum manganese mixed metal oxides(LMMO)regulated via a facile ionic liquid(IL)-assisted hydrothermal method was proposed to construct the multifunctional catalysts,which exhibited excellent catalytic performance in the selective aerobic oxidation of cyclohexane.An 8.9%cyclohexane conversion with 90%KA oi(cyclohexanol and cyclohexanone)selectivity was achieved over the optimal LMMO catalyst under mild conditions.The effects of anion type,carbon chain length and concentration of ILs on the structure and properties of catalysts were investigated through various characterizations,indicating the structure-directing and template effect of ILs on the multifunctional catalysts.The formation of self-assembled spherical nanoparticles followed the"dissolution-nucleation-proliferation"mechanism with the introduction of 1-butyl-3-methylimidazolium hydrogen sulfate,ascribing the synergistic effect between the microenvironment of ILs and the hydrothermal environment.Importantly,the high reactive oxygen concentration redox capacity,and suitable basic sites of LMMO catalysts mediated by ILs enhance the activation of C-H bonds and molecular oxygen,simultaneously influencing the adsorption and desorption of the substrate.A comprehensive understanding of the high KA oil selectivity and radical reaction mechanism was elucidated based on in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and radical trapping experiments.The recycling and regeneration experiments further illuminated that the removal of adsorbed cyclohexanone acting on the LMMO catalyst was the key to achieve high KA oil selectivity.展开更多
Silkworm pupa protein(SPP)that obtained by traditional method usually had a high fat content,which would impose restrictions on the further use of SPP.Herein,various functionalized ionic liquids(ILs)were used to extra...Silkworm pupa protein(SPP)that obtained by traditional method usually had a high fat content,which would impose restrictions on the further use of SPP.Herein,various functionalized ionic liquids(ILs)were used to extract SPP from silkworm pupae,the structure-performance relationship of ILs with their SPP separation performance were explored at the same time.The research showed that the maximum extraction yield of SPP was up to 62.6%with less than 0.5%low fat content by using 1-ethyl-3-methylimidazolium chloride([Emim]Cl),when the dissolution experiment was conducted at 90°C for 24 h with ethanol bath as the regeneration solvent.Comparing with the structure of raw material,the regenerated SPP maintained the native protein backbone.Meanwhile,all regenerated SPP showed a decreased crystallinity,which also exhibited decreased fraction of theα-helix comparing to thatβ-sheet united with coil random structures.展开更多
Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a...Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a mesoporous CeO_(2)single-crystal formed with the regulation of ionic liquids,which catalyzed the effective carbonylation reaction with CO_(2)under mild reaction conditions.By altering the synthetic environment,a series of uniform mesoporous CeO_(2)particles with atomically aligned single-crystal frameworks were constructed,which have different surface physicochemical properties and primary aggregation degree.The prepared mesoporous CeO_(2)single-crystal achieved efficient activation of CO_(2)and alcohols at 0.5 MPa CO_(2)and 100℃,and the CeO_(2)-IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g^(–1)h^(–1),which was 50.6 times as high as that of the CeO_(2)obtained without ionic liquids.Subsequently,the catalytic pathway and mechanism of carbonylation reaction with CO_(2)on mesoporous CeO_(2)single-crystal were studied via React-IR spectra and C18O_(2)labeling experiments.The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials,aiming to develop novel catalytic materials to meet industrial needs.展开更多
COcapture with ionic liquids（ILs） has attracted many attentions, and most works focused on absorption ability at ambient temperatures, while seldom research was concerned at elevated temperatures.This not only limit...COcapture with ionic liquids（ILs） has attracted many attentions, and most works focused on absorption ability at ambient temperatures, while seldom research was concerned at elevated temperatures.This not only limits the COabsorption application at elevated temperature, but also the determination of the operation condition of the COdesorption generally occurring at higher temperature. This work mainly reported COsolubilities in ILs at elevated temperatures and related properties were also provided. 1-alkyl-3-methylimidazolium bis（trifluoromethylsulfonyl）imide（[CnMIm][TfN]） ILs were selected as physical absorbents for COcapture in this work due to their relative higher COabsorption capacities and good thermal stabilities. The long-term stability tests showed that [CnMIm][TfN] is thermally stable at 393.15 K for long time. COsolubilities in [CnMIm][TfN] were systematically determined at temperatures from 353.15 K to 393.15 K. It demonstrated that COsolubility obviously increases with the increase of pressure while slightly decreases with increase of temperature. As the length of alkyl chain on the cation increases, COsolubility in ILs increases. Additionally, the thermodynamic properties including the Gibbs free energy, enthalpy, and entropy of COwere also calculated.展开更多
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supported by the National Key Research and Development Program of China(2022YFB3504702)support from Horizon-EIC,Pathfinder challenges(101070976)+3 种基金support from the National Natural Science Foundation of China(22278402,22478389)the Key Research and Development Program of Henan Province(231111241800)State Key Laboratory of Mesoscience and Engineering(MESO-23-A08)the Frontier Basic Research Projects of Institute of Process Engineering,CAS(QYJC-2023-03).
文摘Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.
基金Supported by the National Basic Research Program of China (2009CB219901)the National Key Technology Research and Development Program of the Ministry of Science and Technology of China (2012BAF03B01)+1 种基金the National Natural Science Foundation of China (20906096,20873152)the Open-end Fund of State Key Laboratory of Multiphase Complex Systems (MPCS-2011-D-06)
文摘Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids were used as promising elec-trolytes in the low-temperature electrodeposition of aluminium.Systematic studies on deposition process have been performed by cyclic voltammetry and chronoamperometry.The surface morphology and X-ray diffraction(XRD) patterns of deposits prepared at different experimental conditions were also investigated.It was shown that the nu-cleation density and growth rate of crystallites had a great effect on the structure of aluminium deposited.The crys-tallographic orientation of deposits was mainly influenced by temperature and current density.Smooth,dense and well adherent aluminium coatings were obtained on copper substrates at 10-25 mA?cm?2 and 313.2-353.2 K.More-over,the current efficiency of deposition and purity of aluminium have been significantly improved,demonstrating that the ionic liquids tested have a prospectful potential in electroplating and electrorefining of aluminium.
基金supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600903)the National Natural Science Foundation of China(91434107,21506226,21476245)the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDY-SSW-JSC011)~~
文摘A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.
基金Supported by the Key Program of National Natural Science Foundation of China (21036007)the National High Technology Research and Development Program of China (2011AA050606)
文摘Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.
基金the National Key Projects for Fundamental Research and Development of China (No. 2016YFB0601303)the Key Research Program of Frontier Sciences (No. QYZDBSSW-SLH022)+3 种基金the International Cooperation and Exchange of the National Natural Science Foundation of China (No. 51561145020)Key Program of National Natural Science Foundation of China (No. 91434203)National Natural Science Foundation of China (No. 21676270)NSFC-Key Projects of Shanxi Coal Based Low Carbon Joint Fundation (No. U1610222)
文摘α, β-unsaturated esters were often synthesized from aldehydes and esters in the presence of strong organic base that was very sensitive to air and moisture via aldol reaction. Trioxane was very useful C1 resource, however, the decomposition of it was always the challenging problem that facing researchers. Herein, a novel synthetic methodology for α, β-unsaturated ester preparation from trioxane and ester with mild catalysis of generated ammonium trifluoromethanesulfonate ionic liquid. The enolization of ester as well as the decomposition of trioxane could proceed easily in the presence of boryl trifluoromethanesulfonate and amine at 20–25℃. Then the enolate and decomposed formaldehyde occurs aldol reaction to form α, β-unsaturated ester. With this strategy, the yield and selectivity of product from various substrates including aliphatic esters,lactones and thioester could reach up to 85.2% and 90.1%.
基金supported by the Science Fund for Major Program of National Natural Science Foundation of China(21890762)Innovation Academy for Green Manufacture,Chinese Academy of Sciences(IAGM-2020-C28).
文摘In light of the increasing demand for environmental protection and energy conservation,the recovery of highly valuable metals,such as Li,Co,and Ni,from spent lithium-ion batteries(LIBs)has attracted widespread attention.Most conventional recycling strategies,however,suffer from a lack of lithium recycling,although they display high efficiency in the recovery of Co and Ni.In this work,we report an efficient extraction process of lithium from the spent LIBs by using a functional imidazolium ionic liquid.The extraction efficiency can be reached to 92.5%after a three-stage extraction,while the extraction efficiency of Ni-Co-Mn is less than 4.0%.The new process shows a high selectivity of lithium ion.FTIR spectroscopy and ultraviolet are utilized to characterize the variations in the functional groups during extraction to reveal that the possible extraction mechanism is cation exchange.The results of this work provide an effective and sustainable strategy of lithium recycling from spent LIBs.
基金supported by the National Key R&D Program of China(2018YFB0605804)the National Natural Science Foundation of China(21606237)+2 种基金the Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences(XDA 21030500)the Fund of State Key Laboratory of Multiphase Complex Systems,IPE,CAS(MPCS-2019-A-02)the DNL Cooperation Fund,CAS(DNL180202)。
文摘The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems containing different imidazolium–based ionic liquids(ILs),i.e.MeOH+DMC+1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf2N]),MeOH+DMC+1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf2N]),and MeOH+DMC+1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])were measured at 101.3 kPa.The mole fraction of IL was varied from0.05 to 0.20.The experimental data were correlated with the NRTL and Wilson equations,respectively.The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and[Bmim][Tf2 N]showed a much more excellent performance on the activity coefficient of MeOH.The interaction energies of system components were calculated using Gaussian program,and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.
基金supported by the One Hundred Talent Program of CASthe National Natural Science Foundation of China Petroleum & Chemical Corporation Joint Fund(U1662129)+1 种基金the National Natural Science Foundation of China(91434203)the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(QYZDY-SSW-JSC011)~~
文摘A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and alcohols under mild conditions.The basic strengths of the ionic liquids were evaluated by determination of their Hammett functions,obtained using ultraviolet‐visible spectroscopy,and the relationship between their catalytic activities and basicities was established.The catalytic efficiencies of the ionic liquids were higher than that of the traditional basic catalyst NaOH.This can be attributed to the involvement of a novel reaction mechanism when these ionic liquids are used.A possible electrophilic‐nucleophilic dual activation mechanism was proposed and confirmed using electrospray ionization quadrupole time‐of‐flight mass spectrometry.In addition,the effects of significant reaction parameters such as concentration of catalyst,molar ratio of alcohol to propylene oxide,reaction temperature,and steric hindrance of the alcohol were investigated in detail.
基金We thank the financial support of Major Program of National Natural Science Foundation of China(21890762)General Program of National Natural Science Foundation of China(21878293)+2 种基金National Natural Science Foundation of China(21676270)Key Research Program of Frontier Sciences,CAS(QYZDY-SSW-JSC011)the K.C.Wong Education Foundation(GJTD-2018-04).
文摘An ionic liquid(IL)catalyzed solvent-free process was developed for the direct synthesis of chalcone and its derivatives by using substituted acetophenones and benzaldehydes via aldol reaction under mild conditions.A series of acidic and basic ILs were selected and screened.The influences of cations and reaction conditions on product yield and selectivity were systematically investigated.The[Bmim]OH was identified as the optimal IL,with the highest yield and selectivity reaching up to 96.7% and 100%,respectively.A reaction mechanism-based kinetic model was established and regressed with experimental data,revealing the β-Hydroxylketone dehydrolysis with activation barrier of 37.8 kJ·mol^(-1) was observed as the ratecontrolling step.
基金Financial support from National Natural Science Foundation of China (22078336, U1662133, 21773158, 22008238)Innovation Academy for Green Manufacture, CAS (IAGM2020C13) is gratefully acknowledged
文摘The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).
基金support of the Startup Foundation of China(3160011181808)the National Natural Scientific Foundation of China(21878292,81673400)K.C.Wong Education Foundation(GJTD-2018-04).
文摘Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.
基金supported by the National Key R&D Program of China(2020YFA0710200)the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(21921005)+2 种基金the Major Scientific and Technological Project of Shanxi Province of China(20201102005)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2020047)the Innovation Academy for Green Manufacture,Chinese Academy of Sciences(IAGM2020C15)。
文摘The separation of carbon dioxide(CO_(2))is of great importance for environment protection and gas resource purification.The ionic liquids(ILs)-based gas separation membrane provides a new chance for efficient CO_(2)separation,while high permeability and selectivity of membranes is a great challenge.In this study,the influence of two protic ILs with different anion([TMGH][Im]and[TMGH][PhO])on the CO_(2)separation performance of the prepared ILs/Pebax blended membranes were systematically investigated at different temperature.The results showed the CO_(2)permeability exhibits the rising trend for ILs/Pebax blended membranes with the increment of IL content.Especially,the[TMGH][Im]with low viscosity and high CO_(2)absorption capacity leads to the blended membranes showing better CO_(2)permeability and ideal CO_(2)selectivity than that of membranes with[TMGH][PhO]at high IL content.Besides,with operating temperature increasing,the gas permeability of 20%(mass)[TMGH][Im]/Pebax blended membrane increases due to the decreasing viscosity of IL and the rising chain mobility of polymer.Inversely,the gas selectivity shows decreasing trend because CO_(2)absorption capacity obviously decreased at higher temperature.
基金financially supported by National Key Research and Develop Program of China (2017YFA0206803)National Science Fund for Excellent Young Scholars (21722610)+2 种基金National Natural Science Foundation of China (21676277)Key Program of National Natural Science Foundation of China (91434203)CAS-SAFEA International PartnershipProgramforCreativeResearchTeams (20140491518)
文摘Mathematical modeling for nanofiltration of ionic liquids(ILs) solutions could assist to understand transfer mechanism and predict experimental values. In this work, modeling by solution-diffusion model for nanofiltration of long-alkyl-chain ILs aqueous solutions was proposed. Molecular simulations were performed to validate the existence of ion cluster in long-alkyl-chain ILs aqueous solution. Based on the results of simulations, parameters used in the solution-diffusion model were modified, such as concentration of ILs and diameter of ion cluster.The modeling process was developed for three long-alkyl-chain ILs aqueous solutions with different concentrations(1-alkyl-3-methylimidazolium chloride: [C6 mim]Cl, [C8 mim]Cl, [C10 mim]Cl). The calculated values obtained from modified solution-diffusion model could well match the experimental values.
基金support from European Union’s Horizon 2020 research,innovation programme under grant agreement No. 958174, Vinnova (Swedish Governmental Agency for Innovation Systems)the financial support from the LTU CREATERNITY program+2 种基金the J. Gust Richert Foundationthe Swedish Energy Agency,STINT (CH2019-8287),and Bio4energythe National Natural Science Foundation of China (No.U23A20122)。
文摘The confined ionic liquid(IL) in solid polymer composite electrolytes(SCPEs) can improve the performance of lithium metal batteries. However, the impact/role and working mechanism of confined IL in SCPEs remain ambiguous. Herein, IL was immobilized on SiO_(2)(SiO_(2)@IL-C) and then used to prepare the confined SCPEs together with LiTFSI and PEO to study the impacts of confined-IL on the properties and performance of electrolytes and reveal the Li+transport mechanism. The results show that, compared to the IL-unconfined SCPE, the IL-confined ones exhibit better performance of electrolytes and cells, such as higher ionic conductivity, higher t+Li, and wider electrochemical windows, as well as more stable cycle performance, due to the increased dissociation degree of lithium salt and enlarged polymer amorphousness. The finite-element/molecular-dynamics simulations suggest that the IL confined on the SiO_(2) provided an additional Li+transport pathway(Li+→ SiO_(2)@IL-C) that can accelerate ion transfer and alleviate lithium dendrites, leading to ultrastable stripping/plating cycling over 1900 h for the Li/SCPEs/Li symmetric cells. This study demonstrates that IL-confinement is an effective strategy for the intelligent approach of high-performance lithium metal batteries.
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financially supported by the National Science Fund for Excellent Young Scholars(No.22222813)the National Natural Science Foundation of China(No.22078338)+1 种基金the Key Scientific and Technological Projects in Huizhou(No.2021JBZ5.1)the Joint Fund of Yulin University and the Dalian National Laboratory for Clean Energy(No.YLU-DNL Fund2021016)。
文摘Selective oxidation of alkanes to produce highvalue chemicals is an essential strategy and means to realize efficient utilization of resources.In this work,a strategy of lanthanum manganese mixed metal oxides(LMMO)regulated via a facile ionic liquid(IL)-assisted hydrothermal method was proposed to construct the multifunctional catalysts,which exhibited excellent catalytic performance in the selective aerobic oxidation of cyclohexane.An 8.9%cyclohexane conversion with 90%KA oi(cyclohexanol and cyclohexanone)selectivity was achieved over the optimal LMMO catalyst under mild conditions.The effects of anion type,carbon chain length and concentration of ILs on the structure and properties of catalysts were investigated through various characterizations,indicating the structure-directing and template effect of ILs on the multifunctional catalysts.The formation of self-assembled spherical nanoparticles followed the"dissolution-nucleation-proliferation"mechanism with the introduction of 1-butyl-3-methylimidazolium hydrogen sulfate,ascribing the synergistic effect between the microenvironment of ILs and the hydrothermal environment.Importantly,the high reactive oxygen concentration redox capacity,and suitable basic sites of LMMO catalysts mediated by ILs enhance the activation of C-H bonds and molecular oxygen,simultaneously influencing the adsorption and desorption of the substrate.A comprehensive understanding of the high KA oil selectivity and radical reaction mechanism was elucidated based on in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and radical trapping experiments.The recycling and regeneration experiments further illuminated that the removal of adsorbed cyclohexanone acting on the LMMO catalyst was the key to achieve high KA oil selectivity.
基金supported financially by the National Natural Science Foundation of China(Nos.81673400 and 21878292)。
文摘Silkworm pupa protein(SPP)that obtained by traditional method usually had a high fat content,which would impose restrictions on the further use of SPP.Herein,various functionalized ionic liquids(ILs)were used to extract SPP from silkworm pupae,the structure-performance relationship of ILs with their SPP separation performance were explored at the same time.The research showed that the maximum extraction yield of SPP was up to 62.6%with less than 0.5%low fat content by using 1-ethyl-3-methylimidazolium chloride([Emim]Cl),when the dissolution experiment was conducted at 90°C for 24 h with ethanol bath as the regeneration solvent.Comparing with the structure of raw material,the regenerated SPP maintained the native protein backbone.Meanwhile,all regenerated SPP showed a decreased crystallinity,which also exhibited decreased fraction of theα-helix comparing to thatβ-sheet united with coil random structures.
文摘Catalysts for CO_(2)value-added conversion have been extensively explored,but there is still a lack of systematic design for catalysts that achieve efficient CO_(2)conversion under mild conditions.Herein,we explored a mesoporous CeO_(2)single-crystal formed with the regulation of ionic liquids,which catalyzed the effective carbonylation reaction with CO_(2)under mild reaction conditions.By altering the synthetic environment,a series of uniform mesoporous CeO_(2)particles with atomically aligned single-crystal frameworks were constructed,which have different surface physicochemical properties and primary aggregation degree.The prepared mesoporous CeO_(2)single-crystal achieved efficient activation of CO_(2)and alcohols at 0.5 MPa CO_(2)and 100℃,and the CeO_(2)-IL-M catalyst shows optimal catalytic performance in the synthesis of ethylene carbonate with 46.22 mmol g^(–1)h^(–1),which was 50.6 times as high as that of the CeO_(2)obtained without ionic liquids.Subsequently,the catalytic pathway and mechanism of carbonylation reaction with CO_(2)on mesoporous CeO_(2)single-crystal were studied via React-IR spectra and C18O_(2)labeling experiments.The research provides a new strategy for controllable nanoscale assembly of mesoporous single-crystal materials and expands the application range of single-crystal materials,aiming to develop novel catalytic materials to meet industrial needs.
基金supported by the National Natural Science Foundation of China (21606233, 21436010)the National Natural Science Fund for Distinguished Young Scholars (21425625)the Research Council of Norway through the CLIMIT program (215732)
文摘COcapture with ionic liquids（ILs） has attracted many attentions, and most works focused on absorption ability at ambient temperatures, while seldom research was concerned at elevated temperatures.This not only limits the COabsorption application at elevated temperature, but also the determination of the operation condition of the COdesorption generally occurring at higher temperature. This work mainly reported COsolubilities in ILs at elevated temperatures and related properties were also provided. 1-alkyl-3-methylimidazolium bis（trifluoromethylsulfonyl）imide（[CnMIm][TfN]） ILs were selected as physical absorbents for COcapture in this work due to their relative higher COabsorption capacities and good thermal stabilities. The long-term stability tests showed that [CnMIm][TfN] is thermally stable at 393.15 K for long time. COsolubilities in [CnMIm][TfN] were systematically determined at temperatures from 353.15 K to 393.15 K. It demonstrated that COsolubility obviously increases with the increase of pressure while slightly decreases with increase of temperature. As the length of alkyl chain on the cation increases, COsolubility in ILs increases. Additionally, the thermodynamic properties including the Gibbs free energy, enthalpy, and entropy of COwere also calculated.
