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
Vapor pressures were measured for six binary systems containing water, ethanol, or methanol with one of the two ionic liquids(ILs) at different component concentrations and temperatures using a quasi-static ebulliomet...Vapor pressures were measured for six binary systems containing water, ethanol, or methanol with one of the two ionic liquids(ILs) at different component concentrations and temperatures using a quasi-static ebulliometer,with the ILs mono-ethanolammonium formate([HMEA][HCOO]) and di-ethanolammonium formate([HDEA][HCOO]).The vapor pressures of the IL-containing binary systems are well correlated using the NRTL model with an overall average absolute relative deviation(AARD) of 0.0062. The effect of ILs on the vapor pressure depression of solvents at 0.050 mole fraction of IL is that [HDEA][HCOO]>[HMEA][HCOO], and the vapor pressure lowering degree follows the order of water>methanol>ethanol. Further, the activity coefficients of three solvents(viz. water,ethanol, and methanol) for the binary systems {solvent(1) + IL(2)} predicted based on the fitted NRTL parameters at T 333.15 K indicate that the two ILs generate a negative deviation from Raoult's law for water and methanol and a positive deviation for ethanol to a varying degree, change the relative volatility of a solvent. [HMEA][HCOO]may be a promising entrainer to efficiently separate ethanol aqueous solutions by special rectification.展开更多
The watermiscible room temperature ionic liquid 1butyl3methylimidazolium tetrafluorob orate （[bmim] [BF4]） is a model system for studying the interactions between ionic liquid and water molecules. In this work the o...The watermiscible room temperature ionic liquid 1butyl3methylimidazolium tetrafluorob orate （[bmim] [BF4]） is a model system for studying the interactions between ionic liquid and water molecules. In this work the orientational structure of the low concentrated aqueous solution of [bmim] [BF4] at the air/liquid interface was investigated by sum frequency gener ation vibrational spectroscopy. It has been found that at very low concentrations, the butyl chain exhibited a significant gauche defect, indicating a disordered conformation; and the cation ring oriented with a fairly small tilting angle at the surface. When the concentration increased, the cation ring tended to lie flat at the surface, and the gauche defects of the butyl chain decreased due to the intermolecular chainchain interactions and the consequent more ordered interfacial molecular arrangement. Additionally, the antisymmetric stretching mode in the PPP and SPS spectra exhibited a peak shift, showing that there exists more than one kind of orientation or chemical environment for the butyl CH3 group. These results may shed new light on understanding the surface behavior of watermiscible ionic liquids as well as the imidazolium based surfactants.展开更多
Hydrothermal liquefaction of wheat straw in sub-critical water with ionic liquid was investigated in an autoclave. The product distribution at different temperatures and pressures was studied. The liquid oil and the r...Hydrothermal liquefaction of wheat straw in sub-critical water with ionic liquid was investigated in an autoclave. The product distribution at different temperatures and pressures was studied. The liquid oil and the residuals were tested by 1H NMR, FTIR and SEM techniques. The results indicated that under the same conditions, the oil yield from liquefaction of wheat straw in water/ethanol was higher than that in sub-critical water. The result also showed that under the investigated conditions, adding 1-butyl-3-methylimidazolium chloride([Bmim]Cl) could increase the total conversion and gas yield, while at the same time the yield of n-hexane insoluble fraction and the tetrahydrofuran soluble fraction was reduced. Moreover, the results also showed that upon adding [Bmim]Cl the contents of the aliphatic hydrogen and phenols in liquid oil also increased along with improved oil quality.展开更多
The application of ionic liquids as alternatives to conventional organic solvents in the extraction process has been investigated. In the present study, fourteen species of imidazolium-based ionic liquids were added i...The application of ionic liquids as alternatives to conventional organic solvents in the extraction process has been investigated. In the present study, fourteen species of imidazolium-based ionic liquids were added into the NaOH （aq） to remove the mercaptans. The influences of anion species and cation alkyl chain length of the imidazolium-based ionic liquids on the performance of mercaptan removal from light oils have been discussed. The efficiency of extraction for mercaptans exhibited the order of [Ac]- 〉 [OH]- [Br]- 〉 [BF4]-. The longer alkyl chain imidazolium-based ionic liquids contributed to enhance desulfurization rate of l-butyl mercaptan. 100% desulfurization rate of l-butyl mercaptan was achieved by the anion of Ac- ionic liquids and NaOH （aq） at a volume ratio of 40：1 （V（oil]：Vfionic liouid）） and a short eouilibrium time within 10 min.展开更多
This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for...This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for the ternary systems Na Cl–[C6mim][Cl](1-hexyl-3-methylimidazolium chloride)–H2O, [C6mim][BF4]–[C6mim][Cl]–H2O,Na NO3–[C6mim][BF4](1-hexyl-3-methylimidazolium tetrafluoroborate)–H2O, and [C4mim][BF4](1-butyl-3-methylimidazolium tetrafluoroborate)–[C6mim][BF4]–H2O, and their binary subsystems NaN O3–H2O, NaC l–H2O,[C6mim][BF4]–H2O, [C6mim][Cl]–H2O, and [C4mim][BF4]–H2O, respectively. The conductivities of the ternary systems were also determined using generalized Young's rule and semi-ideal solution theory in terms of the data of their binary solutions. The comparison showed that the two simple equations provide good predictions for conductivity of mixed electrolyte solutions and the mixed ionic liquid solutions based on the conductivity of their binary subsystems.展开更多
This paper studies the reaction between alkaline metal ions Li＋, Na＋ and K＋ and ASR （alkali-silica reaction） reactive aggregates to determine whether Li＋ can substitute Na＋ and K＋ that are unified in cement pa...This paper studies the reaction between alkaline metal ions Li＋, Na＋ and K＋ and ASR （alkali-silica reaction） reactive aggregates to determine whether Li＋ can substitute Na＋ and K＋ that are unified in cement paste. Reactive aggregates use meta-sandstone from eastern Taiwan and Pyrex glass. Non-reactive aggregates use siliceous sand. The results show that the dissolved amount of SiO2 is lower when the reactive aggregates are immersed in an 80 ℃1 N LiOH＇H20 solution than in NaOH and KOH solutions. The reduced amounts of OH and Li＋ in the solution are also higher than those in the NaOH and KOH solutions. These results reveal that reactive SiO2 can react with LiOH to form a reactant with low water solubility. When the powder of the cement paste is immersed in an 80 ℃ 1 N LiOH-H2O solution, the amounts of free Na＋ and K＋ in the solution are higher than those in water. The increased amount increases with the duration of immersion. The amount of Li＋ in the solution also decreases with the duration of immersion. These results reveal that Li＋ can substitute Na＋ and K＋ that are unified in cement paste, which indicates that ASR can be prevented with the existence of Li＋.展开更多
In this work, 16 kinds of [FeCl4]--based magnetic ionic liquids （ILs） with different cation structures have been designed and synthesized, and their structures are characterized by IR and Raman spectroscopy. Then th...In this work, 16 kinds of [FeCl4]--based magnetic ionic liquids （ILs） with different cation structures have been designed and synthesized, and their structures are characterized by IR and Raman spectroscopy. Then the lower critical solution temperature （LCST）-type phase behavior of these magnetic ILs in water is investigated as a function of concentration. It is shown that cat- ion structure, alkyl chain length and molar ratio of FeCl3/chloride IL have a significant influence on the LCST of the mixtures. The phase separation temperature can be tuned efficiently by these factors. Meanwhile, the LCST-type phase separation pro- cess is also investigated by dynamic light scattering. The results support the mechanism that the hydrogen bonds of the [Fefl4]- anion with water have been gradually disrupted to form ILs aggregates with increasing temperature. In addition, the stability of the ILs in water is also examined in some details. These LCST-type phase separation systems may have potential applications in extraction and separation techniques at room temperature.展开更多
Novel flowerlike Cu20 micro-nanocrystals were prepared by a greener reductive reaction of cupric acetate monohydrate with ethylene glycol in aqueous solutions of [C8mim]X （X = CI-, Br-, BF4-, PFr-） and [C,,mim][BF4]...Novel flowerlike Cu20 micro-nanocrystals were prepared by a greener reductive reaction of cupric acetate monohydrate with ethylene glycol in aqueous solutions of [C8mim]X （X = CI-, Br-, BF4-, PFr-） and [C,,mim][BF4] （n = 4, 6, 8）. The obtained mi- crostructures of Cu2O were characterized by Scanning Electron Microscopy （SEM）, X-ray diffraction （XRD） and Fourier Transform Infrared （FT-IR）. The effects of cations, anions and concentration of the ionic liquids on the morphology of Cu20 were examined in some details. The results suggest that the formation of flowerlike Cu20 was governed by a [Csmim][BF4] controlled reductive reaction mechanism. As one of their applications, the Cu20 nanoparticles were used for the photocatalytic degradation of methylene blue in aqueous solution, and high photocatalytic activity was observed.展开更多
Ion pair speciation of ionic liquids(ILs) has an important effect on the physical and chemical properties of ILs and recognition of the structure of ion pairs in solution is essential. It has been reported that ion pa...Ion pair speciation of ionic liquids(ILs) has an important effect on the physical and chemical properties of ILs and recognition of the structure of ion pairs in solution is essential. It has been reported that ion pairs of some ILs can be formed by hydrogen bonding interactions between cations and anions of them. Considering the fact that far-IR(FIR) spectroscopy is a powerful tool in indicating the intermolecular and intramolecular hydrogen bonding, in this work, this spectroscopic technique has been combined with molecular dynamic(MD) simulation and nuclear magnetic resonance hydrogen spectroscopy(~1H NMR) to investigate ion pairs of aprotic ILs [Bmim][NO_3], [BuPy][NO_3], [Pyr_(14)][NO_3], [PP_(14)][NO_3] and [Bu-choline][NO_3] in aqueous IL mixtures. The FIR spectra have been assigned with the aid of density functional theory(DFT) calculations, and the results are used to understand the effect of cationic nature on the structure of ion pairs. It is found that contact ion pairs formed in the neat aprotic ILs by hydrogen bonding interactions between cation and anion, were still maintained in aqueous solutions up to high water mole fraction(say 0.80 for [BuPy][NO3]). When water content was increased to a critical mole fraction of water(say 0.83 for [BuPy][NO3]), the contact ion pairs could be transformed into solvent-separated ion pairs due to the formation of the hydrogen bonding between ions and water. With the further dilution of the aqueous ILs solution, the solvent-separated ion pairs was finally turned into free cations and free anions(fully hydrated cations or anions). The concentrations of the ILs at which the contact ion pairs were transformed into solvent-separated ion pairs and solvent-separated ion pairs were transformed into free ions(fully hydrated ion) were dependent on the cationic structures. These information provides direct spectral evidence for ion pair structures of the aprotic ILs in aqueous solution. MD simulation and ~1H NMR results support the conclusion drawn from FIR spectra investigations.展开更多
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Supported by the National Natural Science Foundation of China （21076005） and Research Fund for the Doctoral Program of Higher Education of China （20090010110001）.
文摘Vapor pressures were measured for six binary systems containing water, ethanol, or methanol with one of the two ionic liquids(ILs) at different component concentrations and temperatures using a quasi-static ebulliometer,with the ILs mono-ethanolammonium formate([HMEA][HCOO]) and di-ethanolammonium formate([HDEA][HCOO]).The vapor pressures of the IL-containing binary systems are well correlated using the NRTL model with an overall average absolute relative deviation(AARD) of 0.0062. The effect of ILs on the vapor pressure depression of solvents at 0.050 mole fraction of IL is that [HDEA][HCOO]>[HMEA][HCOO], and the vapor pressure lowering degree follows the order of water>methanol>ethanol. Further, the activity coefficients of three solvents(viz. water,ethanol, and methanol) for the binary systems {solvent(1) + IL(2)} predicted based on the fitted NRTL parameters at T 333.15 K indicate that the two ILs generate a negative deviation from Raoult's law for water and methanol and a positive deviation for ethanol to a varying degree, change the relative volatility of a solvent. [HMEA][HCOO]may be a promising entrainer to efficiently separate ethanol aqueous solutions by special rectification.
文摘The watermiscible room temperature ionic liquid 1butyl3methylimidazolium tetrafluorob orate （[bmim] [BF4]） is a model system for studying the interactions between ionic liquid and water molecules. In this work the orientational structure of the low concentrated aqueous solution of [bmim] [BF4] at the air/liquid interface was investigated by sum frequency gener ation vibrational spectroscopy. It has been found that at very low concentrations, the butyl chain exhibited a significant gauche defect, indicating a disordered conformation; and the cation ring oriented with a fairly small tilting angle at the surface. When the concentration increased, the cation ring tended to lie flat at the surface, and the gauche defects of the butyl chain decreased due to the intermolecular chainchain interactions and the consequent more ordered interfacial molecular arrangement. Additionally, the antisymmetric stretching mode in the PPP and SPS spectra exhibited a peak shift, showing that there exists more than one kind of orientation or chemical environment for the butyl CH3 group. These results may shed new light on understanding the surface behavior of watermiscible ionic liquids as well as the imidazolium based surfactants.
基金the Research Fund for the Doctoral Program of Higher Education for new teachers of China(20091404120002)the Shanxi Province Science Foundation for Youths of China(2011021008-1)the Soft Science Program of Shanxi Province(2011041015-01)
文摘Hydrothermal liquefaction of wheat straw in sub-critical water with ionic liquid was investigated in an autoclave. The product distribution at different temperatures and pressures was studied. The liquid oil and the residuals were tested by 1H NMR, FTIR and SEM techniques. The results indicated that under the same conditions, the oil yield from liquefaction of wheat straw in water/ethanol was higher than that in sub-critical water. The result also showed that under the investigated conditions, adding 1-butyl-3-methylimidazolium chloride([Bmim]Cl) could increase the total conversion and gas yield, while at the same time the yield of n-hexane insoluble fraction and the tetrahydrofuran soluble fraction was reduced. Moreover, the results also showed that upon adding [Bmim]Cl the contents of the aliphatic hydrogen and phenols in liquid oil also increased along with improved oil quality.
文摘The application of ionic liquids as alternatives to conventional organic solvents in the extraction process has been investigated. In the present study, fourteen species of imidazolium-based ionic liquids were added into the NaOH （aq） to remove the mercaptans. The influences of anion species and cation alkyl chain length of the imidazolium-based ionic liquids on the performance of mercaptan removal from light oils have been discussed. The efficiency of extraction for mercaptans exhibited the order of [Ac]- 〉 [OH]- [Br]- 〉 [BF4]-. The longer alkyl chain imidazolium-based ionic liquids contributed to enhance desulfurization rate of l-butyl mercaptan. 100% desulfurization rate of l-butyl mercaptan was achieved by the anion of Ac- ionic liquids and NaOH （aq） at a volume ratio of 40：1 （V（oil]：Vfionic liouid）） and a short eouilibrium time within 10 min.
基金Supported by the National Natural Science Foundation of China(51066004)the Scientific Research Project of Higher Education Institutions of Inner Mongolia(NJZY14172)the Innovation Fund of Inner Mongolia Science and Technology(2011NCL060)
文摘This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for the ternary systems Na Cl–[C6mim][Cl](1-hexyl-3-methylimidazolium chloride)–H2O, [C6mim][BF4]–[C6mim][Cl]–H2O,Na NO3–[C6mim][BF4](1-hexyl-3-methylimidazolium tetrafluoroborate)–H2O, and [C4mim][BF4](1-butyl-3-methylimidazolium tetrafluoroborate)–[C6mim][BF4]–H2O, and their binary subsystems NaN O3–H2O, NaC l–H2O,[C6mim][BF4]–H2O, [C6mim][Cl]–H2O, and [C4mim][BF4]–H2O, respectively. The conductivities of the ternary systems were also determined using generalized Young's rule and semi-ideal solution theory in terms of the data of their binary solutions. The comparison showed that the two simple equations provide good predictions for conductivity of mixed electrolyte solutions and the mixed ionic liquid solutions based on the conductivity of their binary subsystems.
文摘This paper studies the reaction between alkaline metal ions Li＋, Na＋ and K＋ and ASR （alkali-silica reaction） reactive aggregates to determine whether Li＋ can substitute Na＋ and K＋ that are unified in cement paste. Reactive aggregates use meta-sandstone from eastern Taiwan and Pyrex glass. Non-reactive aggregates use siliceous sand. The results show that the dissolved amount of SiO2 is lower when the reactive aggregates are immersed in an 80 ℃1 N LiOH＇H20 solution than in NaOH and KOH solutions. The reduced amounts of OH and Li＋ in the solution are also higher than those in the NaOH and KOH solutions. These results reveal that reactive SiO2 can react with LiOH to form a reactant with low water solubility. When the powder of the cement paste is immersed in an 80 ℃ 1 N LiOH-H2O solution, the amounts of free Na＋ and K＋ in the solution are higher than those in water. The increased amount increases with the duration of immersion. The amount of Li＋ in the solution also decreases with the duration of immersion. These results reveal that Li＋ can substitute Na＋ and K＋ that are unified in cement paste, which indicates that ASR can be prevented with the existence of Li＋.
基金supported by the National Natural Science Foundation of China (21473050, 21403060)Program for Innovative Research Team in Science and Technology in University of Henan Province (16IRTSTHN002)+1 种基金Plan for Scientific Innovation Talent of Henan Province of China (144200510004)the Natural Science Research Program of Henan Educational Committee (2010A150014)
文摘In this work, 16 kinds of [FeCl4]--based magnetic ionic liquids （ILs） with different cation structures have been designed and synthesized, and their structures are characterized by IR and Raman spectroscopy. Then the lower critical solution temperature （LCST）-type phase behavior of these magnetic ILs in water is investigated as a function of concentration. It is shown that cat- ion structure, alkyl chain length and molar ratio of FeCl3/chloride IL have a significant influence on the LCST of the mixtures. The phase separation temperature can be tuned efficiently by these factors. Meanwhile, the LCST-type phase separation pro- cess is also investigated by dynamic light scattering. The results support the mechanism that the hydrogen bonds of the [Fefl4]- anion with water have been gradually disrupted to form ILs aggregates with increasing temperature. In addition, the stability of the ILs in water is also examined in some details. These LCST-type phase separation systems may have potential applications in extraction and separation techniques at room temperature.
基金supported financially by the National Natural Science Foundation of China (21003039)the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (092101510300)the Program for Science & Technology Innovation Talents in Universities of Henan Province (2009HASTIT005)
文摘Novel flowerlike Cu20 micro-nanocrystals were prepared by a greener reductive reaction of cupric acetate monohydrate with ethylene glycol in aqueous solutions of [C8mim]X （X = CI-, Br-, BF4-, PFr-） and [C,,mim][BF4] （n = 4, 6, 8）. The obtained mi- crostructures of Cu2O were characterized by Scanning Electron Microscopy （SEM）, X-ray diffraction （XRD） and Fourier Transform Infrared （FT-IR）. The effects of cations, anions and concentration of the ionic liquids on the morphology of Cu20 were examined in some details. The results suggest that the formation of flowerlike Cu20 was governed by a [Csmim][BF4] controlled reductive reaction mechanism. As one of their applications, the Cu20 nanoparticles were used for the photocatalytic degradation of methylene blue in aqueous solution, and high photocatalytic activity was observed.
基金supported by the National Natural Science Foundation of China(21573060,21673068)Program for Innovative Research Team in Science and Technology in University of Henan Province(16IRTSTHN002)+1 种基金Plan for Scientific Innovation Talent of Henan Province(144200510004)The High Performance Computing Center of Henan Normal University
文摘Ion pair speciation of ionic liquids(ILs) has an important effect on the physical and chemical properties of ILs and recognition of the structure of ion pairs in solution is essential. It has been reported that ion pairs of some ILs can be formed by hydrogen bonding interactions between cations and anions of them. Considering the fact that far-IR(FIR) spectroscopy is a powerful tool in indicating the intermolecular and intramolecular hydrogen bonding, in this work, this spectroscopic technique has been combined with molecular dynamic(MD) simulation and nuclear magnetic resonance hydrogen spectroscopy(~1H NMR) to investigate ion pairs of aprotic ILs [Bmim][NO_3], [BuPy][NO_3], [Pyr_(14)][NO_3], [PP_(14)][NO_3] and [Bu-choline][NO_3] in aqueous IL mixtures. The FIR spectra have been assigned with the aid of density functional theory(DFT) calculations, and the results are used to understand the effect of cationic nature on the structure of ion pairs. It is found that contact ion pairs formed in the neat aprotic ILs by hydrogen bonding interactions between cation and anion, were still maintained in aqueous solutions up to high water mole fraction(say 0.80 for [BuPy][NO3]). When water content was increased to a critical mole fraction of water(say 0.83 for [BuPy][NO3]), the contact ion pairs could be transformed into solvent-separated ion pairs due to the formation of the hydrogen bonding between ions and water. With the further dilution of the aqueous ILs solution, the solvent-separated ion pairs was finally turned into free cations and free anions(fully hydrated cations or anions). The concentrations of the ILs at which the contact ion pairs were transformed into solvent-separated ion pairs and solvent-separated ion pairs were transformed into free ions(fully hydrated ion) were dependent on the cationic structures. These information provides direct spectral evidence for ion pair structures of the aprotic ILs in aqueous solution. MD simulation and ~1H NMR results support the conclusion drawn from FIR spectra investigations.
