REFERENCES [1, 2] prove that ionic radii will increase or decrease with temperature rising orlowering. If the ionic radii at room temperature are known, many phenomena of the ioniccompounds occurring at room temperatu...REFERENCES [1, 2] prove that ionic radii will increase or decrease with temperature rising orlowering. If the ionic radii at room temperature are known, many phenomena of the ioniccompounds occurring at room temperature can be explained. Also if the ionic radii at high tem-perature are known, many phenomena of the ionic compounds occurring at high temperaturecan also be explained. Therefore, to calculate the effective radii of ions at high temperature isconsidered of great significance. For example, the 'investigation of KIO<sub>3</sub>-CsIO<sub>3</sub>展开更多
Volume effect has been extensively investigated in several families of solid electrolytes, i.e., expanding the skeleton lattice by bigger-size substitution favors the ionic conduction. However, this effect is not appl...Volume effect has been extensively investigated in several families of solid electrolytes, i.e., expanding the skeleton lattice by bigger-size substitution favors the ionic conduction. However, this effect is not applicable in α-Li2SO4 and α-Na3PO4 based inorganic ionic plastic crystal electrolytes, a unique family of solid electrolytes. Here, it is proposed that the underlying rotational motion effect of polyanion, which is actually inhibited by the substitution of bigger-size polyanion in single-phase solid solution region and causes the unexpected lowering of the ionic conductivity instead, should need the more consideration. Furthermore, through utilizing the rotational motion effect of polyanion, it is given that a new explanation of the ionic conductivities of Li10MP2S12 （M = Si, Ge, Se） electrolytes deviating from the volume effect. These results inspire new vision of rationalization of the high-performance solid electrolytes by tuning the rotational motion effect of polyanion.展开更多
The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two p...The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equstion. The effect of the ionic size of sir supporting electrolytes on diffusion and electron transfer dynamics of fermcene was discussed展开更多
This paper presents the vapor–liquid equilibrium(VLE) data of acetonitrile–water system containing ionic liquids(ILs) at atmospheric pressure(101.3 k Pa). Since ionic liquids dissociate into anions and cations, the ...This paper presents the vapor–liquid equilibrium(VLE) data of acetonitrile–water system containing ionic liquids(ILs) at atmospheric pressure(101.3 k Pa). Since ionic liquids dissociate into anions and cations, the VLE data for the acetonitrile + water + ILs systems are correlated by salt effect models, Furter model and improved Furter model. The overall average relative deviation of Furter model and improved Furter model is 5.43% and 4.68%, respectively. Thus the salt effect models are applicable for the correlation of IL containing systems. The salting-out effect theory can be used to explain the change of relative volatility of acetonitrile–water system.展开更多
The apparent acid dissociation constant (Kc) of benzoic acid in water has been determined ti-trimetrically under ionic strength values between 0.00 and 0.50 mol·L﹣1 at a range of temperatures between 16°C a...The apparent acid dissociation constant (Kc) of benzoic acid in water has been determined ti-trimetrically under ionic strength values between 0.00 and 0.50 mol·L﹣1 at a range of temperatures between 16°C and 41°C. The thermodynamic dissociation constant (as pKa) of benzoic acid was determined as 4.176 at 25°C. No regular correlation between pKa of benzoic acid and the temperature in the range was used. The values of pKa are inversely proportional to temperatures between 16°C and 30°C. In this range of temperature, the values of thermodynamic quantities () for the dissociation process of benzoic acid in water were calculated by using Van’t Hoff plot. For this case the dissociation was not favoured through entropy and enthalpy changes. The values of pKa are directly proportional to temperatures between 30°C and 41°C.展开更多
Room temperature ionic liquids have been currently used in liquid/liquid extraction processes in order to substitute conventional organic solvents. In this paper, a series of chlorinated solvents and 1-alkyl-3-me- thy...Room temperature ionic liquids have been currently used in liquid/liquid extraction processes in order to substitute conventional organic solvents. In this paper, a series of chlorinated solvents and 1-alkyl-3-me- thylimidazolium-based ionic liquids were selected to study the extraction efficiency of a lipophilic polya- mine 1,1,7,7-tetraethyl-4-tetradecyldiethylenetriamine (TE14DT) towards the model ion Cu(II) in such dif-ferent media. The effect of temperature on the extraction efficiency was also investigated. The metal ion par-tition was found to be strongly dependent on both the nature of the solvent and on the working temperature. The viscosity of ionic liquids and the water content in ionic liquid were found to affect the extraction effi-ciency of TE14DT. The chemical nature of the cation of ionic liquids, and in particular the alkyl chain length on imidazolium ring, also seemed to be important in determining the efficiency of the extraction process. Finally, preliminary experiments on back-extraction of Cu(II) ions from ionic liquid also revealed interesting hints to the development of a continuous transport process.展开更多
Extraction behavior of thorium(Ⅳ) and uranium(Ⅵ) from nitric acid(HNO_3) was studied using N,N,N',N'-tetraoctyldiglycolamide(TODGA) as extractant in different ionic liquids, and isooctane as comparison.Slope...Extraction behavior of thorium(Ⅳ) and uranium(Ⅵ) from nitric acid(HNO_3) was studied using N,N,N',N'-tetraoctyldiglycolamide(TODGA) as extractant in different ionic liquids, and isooctane as comparison.Slope analyses with varying HNO_3 concentrations and diluents revealed the extraction mechanism. With increasing length of alkyl chain and HNO_3 concentration, the extraction mechanism of TODGA/IL system changed from cation exchange to neutral complex and/or anion exchange,and the molar ratio between TODGA and metal ions varied gradually from 2:1 to 1:1 for Th(Ⅳ) and 3:1 to 1:1 for U(Ⅵ). The kinetics and thermodynamic studies of Th(Ⅳ)and U(Ⅵ) by the best TODGA/[C_2mim][NTf_2] system showed that the extraction equilibrium was reached within 2 h and extraction reactions were endothermic. Compared to TODGA/isooctane system, TODGA/[C_2mim][NTf_2]system presented higher radiation stability under c-irradiation. Therefore, it would have a promising application in spent fuel reprocessing.展开更多
A CO<sub>2</sub> capture system without supercritical CO<sub>2</sub> was optimized for mixtures of hydrophobic room temperature ionic liquids (RTILs) and propanol. We tested RTILs using bis(tri...A CO<sub>2</sub> capture system without supercritical CO<sub>2</sub> was optimized for mixtures of hydrophobic room temperature ionic liquids (RTILs) and propanol. We tested RTILs using bis(trifluoromethanesulfonyl)imide, TFSI-, anion and four quaternary ammonium cations, two quaternary phosphonium cations, and one imidazolium cation. The addition of 2-propanol into the RTILs clearly promoted the capture of normal CO<sub>2</sub>(nCO<sub>2</sub>) at ambient temperature and pressure. When combined with 2-propanol, the most efficient RTILs for nCO<sub>2</sub> capture were N-butyl-N,N,N-trimethylammonium TFSI-. This enhancement of nCO<sub>2</sub> capture was not observed in RTIL mixtures with 1-propanol or in propanol mixtures containing other phosphonium- and imidazolium-based RTILs. The torsion angle of TFSI-, which was calculated using density functional theory, is thought to be related to high nCO<sub>2</sub> capture efficiently.展开更多
Salinity-gradient energy,as a crucial renewable energy,can be efficiently and directly transduced into electricity through nanofluidic osmotic energy conversion.Nanofluidic osmotic power generation technology is based...Salinity-gradient energy,as a crucial renewable energy,can be efficiently and directly transduced into electricity through nanofluidic osmotic energy conversion.Nanofluidic osmotic power generation technology is based on nanochannels and employs the“gate effect”of the electrical double layer in nanochannels to generate an ion current.In the conventional partial-factor model for osmotic energy conversion(PF-OEC),the ion is assumed to be a point charge,and the ionic volume and dielectric effects are neglected.The ion concentrations at charged surfaces are overestimated during osmotic power generation.In this study,a full-factor model for osmotic energy conversion(FF-OEC)is established to overcome the point-charge assumption of the conventional model.The steric force,Born force,and dielectrophoretic force are fully incorporated into the model to satisfy the nano-confined scenarios.Based on FF-OEC,a numerical model using the finite element method is further constructed to unravel the ionic volume and dielectric effects.The feasibility of FF-OEC is experimentally verified by measuring the osmotic current and diffusion potential of four monovalent and divalent cations.The full-factor model can capture a more physically realistic electrical double-layer structure,which is more uniform compared to the conventional model.PF-OEC is applicable to nanochannels with large radii(larger than or equal to 5 nm)and low surface charge densities(lower than or equal to 0.04 C m^(-2)).FF-OEC is applicable to nanochannels with various radii and surface charge densities.When the radius decreases or the absolute value of surface charge density increases,PF-OEC underestimates power generation performance,and FF-OEC is required to overcome the underestimation of performance in nano-confined channels.This study enriches the theory of ion-selective transport in nano-confined channels and provides a basis for the device design under multiple environments.展开更多
The micro-channels usually refers to structural channels of minerals with aperture in the range of 0.3 nm to 2.0 nm. Such microchannels include, Mn-O octahedron channel filled by K in cryptomelane, and channel constru...The micro-channels usually refers to structural channels of minerals with aperture in the range of 0.3 nm to 2.0 nm. Such microchannels include, Mn-O octahedron channel filled by K in cryptomelane, and channel constructed by Si-O and AI-O tetragonal molecular sieve filled by Na and Ca in zeolite, and effectively have the function of molecular sieve. Here we point out that ultramicrochannels of natural minerals have apertures below 0.3 nm with the features of ionic sieves. The ultra-microchannels of mineral feldspar, accounting for half mass of the Earth＇s crust, have been largely ignored because the aperture is too small. In this work, we present that feldspar displays a certain degree of ion exchange and owns a feature of channel structure under both high and low temperatures. At high temperature, Na^＋ can enter the channels of feldspars. The content of Na2O in feldspar increases up to 15.9%. At middle temperature, Pb^2＋ can also enter the channels of feldspar as the result of ion exchange, leading thus to the formation of Pb-feldspar. At room temperature, about 97.94% Cd^2＋ can be removed and Cd-feldspar can be obtained. These phenomena indicate typical effects of ultra-microchannels of feldspar, which may be suggested as a potential for the treatment of heavy metal pollution and nuclear waste. The ultra-microchannels of natural minerals have played special role in migration and exchange of geomaterials. The molecular sieves of microchannels of a few natural minerals have the property of purifying molecular gas pollution. And the ionic sieves of ultramicrochannels of most natural minerals can purify ionic water contaminates.展开更多
The performance of an electrocatalyst, which is needed e.g. for key energy conversion reactions such as hydrogen evolution, oxygen reduction or CO2 reduction, is determined not only by the inherent structure of active...The performance of an electrocatalyst, which is needed e.g. for key energy conversion reactions such as hydrogen evolution, oxygen reduction or CO2 reduction, is determined not only by the inherent structure of active sites but also by the properties of the interfacial structures at catalytic surfaces. Ionic liquids（ILs）, as a unique class of metal salts with melting point below 100 ℃, present themselves as ideal modulators for manipulations of the interfacial structures. Due to their excellent properties such as good chemical stability, high ionic conductivity, wide electrochemical windows and tunable solvent properties the performance of electrocatalysts can be substantially improved through ILs. In the current minireview, we highlight the critical role of the IL phase at the microenvironments created by the IL, the liquid electrolyte, catalytic nanoparticles and/or support materials, by detailing the promotional effect of IL in electrocatalysis as reaction media, binders, and surface modifiers. Updated exemplary applications of IL in electrocatalysis are given and moreover, the latest developments of IL modified electrocatalysts following the ＂Solid Catalyst with Ionic Liquid Layer（SCILL）＂ concept are presented.展开更多
文摘REFERENCES [1, 2] prove that ionic radii will increase or decrease with temperature rising orlowering. If the ionic radii at room temperature are known, many phenomena of the ioniccompounds occurring at room temperature can be explained. Also if the ionic radii at high tem-perature are known, many phenomena of the ionic compounds occurring at high temperaturecan also be explained. Therefore, to calculate the effective radii of ions at high temperature isconsidered of great significance. For example, the 'investigation of KIO<sub>3</sub>-CsIO<sub>3</sub>
基金financially supported by the National Natural Science Foundation of China(Nos.U1430104,51622207 and 51372228)the National Key Research and Development Program of China(No.2017YFB0701600)
文摘Volume effect has been extensively investigated in several families of solid electrolytes, i.e., expanding the skeleton lattice by bigger-size substitution favors the ionic conduction. However, this effect is not applicable in α-Li2SO4 and α-Na3PO4 based inorganic ionic plastic crystal electrolytes, a unique family of solid electrolytes. Here, it is proposed that the underlying rotational motion effect of polyanion, which is actually inhibited by the substitution of bigger-size polyanion in single-phase solid solution region and causes the unexpected lowering of the ionic conductivity instead, should need the more consideration. Furthermore, through utilizing the rotational motion effect of polyanion, it is given that a new explanation of the ionic conductivities of Li10MP2S12 （M = Si, Ge, Se） electrolytes deviating from the volume effect. These results inspire new vision of rationalization of the high-performance solid electrolytes by tuning the rotational motion effect of polyanion.
文摘The ditheion coefficients(Dapp) and the heterogeneous electron-transfer rate constan(ks)for ferrocene in MPEG/salt electrolytes were determined by using Steady-stae voltammetry. The temperature dependence of the two parameters obeys the Arrhenius equstion. The effect of the ionic size of sir supporting electrolytes on diffusion and electron transfer dynamics of fermcene was discussed
基金Supported by the National Natural Science Foundation of China(21306036)the Youth Scholars of Educational Commission of Hebei Province of China(Y2012040)the Joint Specialized Research Fund for the Doctoral Program of Higher Education(20131317120014)
文摘This paper presents the vapor–liquid equilibrium(VLE) data of acetonitrile–water system containing ionic liquids(ILs) at atmospheric pressure(101.3 k Pa). Since ionic liquids dissociate into anions and cations, the VLE data for the acetonitrile + water + ILs systems are correlated by salt effect models, Furter model and improved Furter model. The overall average relative deviation of Furter model and improved Furter model is 5.43% and 4.68%, respectively. Thus the salt effect models are applicable for the correlation of IL containing systems. The salting-out effect theory can be used to explain the change of relative volatility of acetonitrile–water system.
文摘The apparent acid dissociation constant (Kc) of benzoic acid in water has been determined ti-trimetrically under ionic strength values between 0.00 and 0.50 mol·L﹣1 at a range of temperatures between 16°C and 41°C. The thermodynamic dissociation constant (as pKa) of benzoic acid was determined as 4.176 at 25°C. No regular correlation between pKa of benzoic acid and the temperature in the range was used. The values of pKa are inversely proportional to temperatures between 16°C and 30°C. In this range of temperature, the values of thermodynamic quantities () for the dissociation process of benzoic acid in water were calculated by using Van’t Hoff plot. For this case the dissociation was not favoured through entropy and enthalpy changes. The values of pKa are directly proportional to temperatures between 30°C and 41°C.
文摘Room temperature ionic liquids have been currently used in liquid/liquid extraction processes in order to substitute conventional organic solvents. In this paper, a series of chlorinated solvents and 1-alkyl-3-me- thylimidazolium-based ionic liquids were selected to study the extraction efficiency of a lipophilic polya- mine 1,1,7,7-tetraethyl-4-tetradecyldiethylenetriamine (TE14DT) towards the model ion Cu(II) in such dif-ferent media. The effect of temperature on the extraction efficiency was also investigated. The metal ion par-tition was found to be strongly dependent on both the nature of the solvent and on the working temperature. The viscosity of ionic liquids and the water content in ionic liquid were found to affect the extraction effi-ciency of TE14DT. The chemical nature of the cation of ionic liquids, and in particular the alkyl chain length on imidazolium ring, also seemed to be important in determining the efficiency of the extraction process. Finally, preliminary experiments on back-extraction of Cu(II) ions from ionic liquid also revealed interesting hints to the development of a continuous transport process.
基金financially supported by the National Natural Science Foundation of China(No.11475112)the Ph.D. Programs Foundation of Ministry of Education of China(No.20130073120051)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning
文摘Extraction behavior of thorium(Ⅳ) and uranium(Ⅵ) from nitric acid(HNO_3) was studied using N,N,N',N'-tetraoctyldiglycolamide(TODGA) as extractant in different ionic liquids, and isooctane as comparison.Slope analyses with varying HNO_3 concentrations and diluents revealed the extraction mechanism. With increasing length of alkyl chain and HNO_3 concentration, the extraction mechanism of TODGA/IL system changed from cation exchange to neutral complex and/or anion exchange,and the molar ratio between TODGA and metal ions varied gradually from 2:1 to 1:1 for Th(Ⅳ) and 3:1 to 1:1 for U(Ⅵ). The kinetics and thermodynamic studies of Th(Ⅳ)and U(Ⅵ) by the best TODGA/[C_2mim][NTf_2] system showed that the extraction equilibrium was reached within 2 h and extraction reactions were endothermic. Compared to TODGA/isooctane system, TODGA/[C_2mim][NTf_2]system presented higher radiation stability under c-irradiation. Therefore, it would have a promising application in spent fuel reprocessing.
文摘A CO<sub>2</sub> capture system without supercritical CO<sub>2</sub> was optimized for mixtures of hydrophobic room temperature ionic liquids (RTILs) and propanol. We tested RTILs using bis(trifluoromethanesulfonyl)imide, TFSI-, anion and four quaternary ammonium cations, two quaternary phosphonium cations, and one imidazolium cation. The addition of 2-propanol into the RTILs clearly promoted the capture of normal CO<sub>2</sub>(nCO<sub>2</sub>) at ambient temperature and pressure. When combined with 2-propanol, the most efficient RTILs for nCO<sub>2</sub> capture were N-butyl-N,N,N-trimethylammonium TFSI-. This enhancement of nCO<sub>2</sub> capture was not observed in RTIL mixtures with 1-propanol or in propanol mixtures containing other phosphonium- and imidazolium-based RTILs. The torsion angle of TFSI-, which was calculated using density functional theory, is thought to be related to high nCO<sub>2</sub> capture efficiently.
基金supported by the National Science Foundation for Distinguished Young Scholars(Grant No.52025065)。
文摘Salinity-gradient energy,as a crucial renewable energy,can be efficiently and directly transduced into electricity through nanofluidic osmotic energy conversion.Nanofluidic osmotic power generation technology is based on nanochannels and employs the“gate effect”of the electrical double layer in nanochannels to generate an ion current.In the conventional partial-factor model for osmotic energy conversion(PF-OEC),the ion is assumed to be a point charge,and the ionic volume and dielectric effects are neglected.The ion concentrations at charged surfaces are overestimated during osmotic power generation.In this study,a full-factor model for osmotic energy conversion(FF-OEC)is established to overcome the point-charge assumption of the conventional model.The steric force,Born force,and dielectrophoretic force are fully incorporated into the model to satisfy the nano-confined scenarios.Based on FF-OEC,a numerical model using the finite element method is further constructed to unravel the ionic volume and dielectric effects.The feasibility of FF-OEC is experimentally verified by measuring the osmotic current and diffusion potential of four monovalent and divalent cations.The full-factor model can capture a more physically realistic electrical double-layer structure,which is more uniform compared to the conventional model.PF-OEC is applicable to nanochannels with large radii(larger than or equal to 5 nm)and low surface charge densities(lower than or equal to 0.04 C m^(-2)).FF-OEC is applicable to nanochannels with various radii and surface charge densities.When the radius decreases or the absolute value of surface charge density increases,PF-OEC underestimates power generation performance,and FF-OEC is required to overcome the underestimation of performance in nano-confined channels.This study enriches the theory of ion-selective transport in nano-confined channels and provides a basis for the device design under multiple environments.
文摘The micro-channels usually refers to structural channels of minerals with aperture in the range of 0.3 nm to 2.0 nm. Such microchannels include, Mn-O octahedron channel filled by K in cryptomelane, and channel constructed by Si-O and AI-O tetragonal molecular sieve filled by Na and Ca in zeolite, and effectively have the function of molecular sieve. Here we point out that ultramicrochannels of natural minerals have apertures below 0.3 nm with the features of ionic sieves. The ultra-microchannels of mineral feldspar, accounting for half mass of the Earth＇s crust, have been largely ignored because the aperture is too small. In this work, we present that feldspar displays a certain degree of ion exchange and owns a feature of channel structure under both high and low temperatures. At high temperature, Na^＋ can enter the channels of feldspars. The content of Na2O in feldspar increases up to 15.9%. At middle temperature, Pb^2＋ can also enter the channels of feldspar as the result of ion exchange, leading thus to the formation of Pb-feldspar. At room temperature, about 97.94% Cd^2＋ can be removed and Cd-feldspar can be obtained. These phenomena indicate typical effects of ultra-microchannels of feldspar, which may be suggested as a potential for the treatment of heavy metal pollution and nuclear waste. The ultra-microchannels of natural minerals have played special role in migration and exchange of geomaterials. The molecular sieves of microchannels of a few natural minerals have the property of purifying molecular gas pollution. And the ionic sieves of ultramicrochannels of most natural minerals can purify ionic water contaminates.
基金supported by the funding of the German Research Council (DFG), which, within the framework of its Excellence Initiative, supports the Cluster of Excellence “Engineering of Advanced Materials” (www.eam.uni-erlangen.de) at the University of Erlangen-Nürnberg
文摘The performance of an electrocatalyst, which is needed e.g. for key energy conversion reactions such as hydrogen evolution, oxygen reduction or CO2 reduction, is determined not only by the inherent structure of active sites but also by the properties of the interfacial structures at catalytic surfaces. Ionic liquids（ILs）, as a unique class of metal salts with melting point below 100 ℃, present themselves as ideal modulators for manipulations of the interfacial structures. Due to their excellent properties such as good chemical stability, high ionic conductivity, wide electrochemical windows and tunable solvent properties the performance of electrocatalysts can be substantially improved through ILs. In the current minireview, we highlight the critical role of the IL phase at the microenvironments created by the IL, the liquid electrolyte, catalytic nanoparticles and/or support materials, by detailing the promotional effect of IL in electrocatalysis as reaction media, binders, and surface modifiers. Updated exemplary applications of IL in electrocatalysis are given and moreover, the latest developments of IL modified electrocatalysts following the ＂Solid Catalyst with Ionic Liquid Layer（SCILL）＂ concept are presented.
