Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or a...Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.展开更多
How to determine accurately the association states of solutes in aqueous systems is of fundamental importance in a variety of chemical, physical, and biological processes, We apply four widely used criteria to analyze...How to determine accurately the association states of solutes in aqueous systems is of fundamental importance in a variety of chemical, physical, and biological processes, We apply four widely used criteria to analyze the dynamic association processes of solutes, e.g., amphiphilic molecules, and to find the inappropriate selections of representative sites on solutes in these criteria may bring about appreciable influence on the estimation of dynamic association behaviors such as unrealistic packing radii and even misleading packing structures. It would be better to select dynamically representative sites on solute molecules based on the characteristic of solute associations. Our detailed discussions give a guide on how to determine an appropriate criterion to accurately analyze the association behaviors of solute molecules in aqueous solutions.展开更多
The adsorption of decylmethylsulfoxide(DEMS)onto carbon black and the effects of temperature,salt(NaCl)and acid (HCl)have been measured.Typical two plateaux type adsorption isotherms were obtained.Applying the two ste...The adsorption of decylmethylsulfoxide(DEMS)onto carbon black and the effects of temperature,salt(NaCl)and acid (HCl)have been measured.Typical two plateaux type adsorption isotherms were obtained.Applying the two step model of surfactant adsorption on solid/liquld interface and the general adsorption isotherm equation[9]the experimental results were interpreted qualitatively and quantitatively.展开更多
Ionic liquids (ILs) have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escap...Ionic liquids (ILs) have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydrate formation. For illustration, the dilute aqueous solutions with concentrations of ILs ranging from 2× 10^-3 mol% to 2×10^-1 mol% were concentrated. The results show that the separation efficiency is very impressive and that the new method is applicable to aqueous solutions of both hydrophobic and hydrophilic ILs. Compared to the literature separation method based on the supercritical CO2, the new method is applicable to lower concentrations, and more importantly, its operation condition is mild.展开更多
Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with...Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with the size down to<1μm sometimes),and record critical physical-chemical signals for the formations of their host minerals.Spectroscopic methods like Raman spectroscopy and infrared spectroscopy have been proposed as effective methods to quantify the carbonate concentrations of these fluid inclusions.Although they have some great technical advantages over the conventional microthermometry method,there are still some technical difficulties to overcome before they can be routinely used to solve relevant geological problems.The typical limitations include their interlaboratory difference and poor performance on micro fluid inclusions.This study prepared standard ion-distilled water and K_(2)CO_(3)aqueous solutions at different molarities(from 0.5 to 5.5 mol/L),measured densities,collected Raman and infrared spectra,and explored correlations between the K_(2)CO_(3)molarity and the spectroscopic features at ambient P-T conditions.The result confirms that the Raman O-H stretching mode can be used as an internal standard to determine the carbonate concentrations despite some significant differences among the correlations,established in different laboratories,between the relative Raman intensity of the C-O symmetric stretching mode and that of the O-H stretching mode.It further reveals that the interlaboratory difference can be readily removed by performing one high-quality calibration experiment,provided that later quantifying analyses are conducted using the same Raman spectrometer with the same analytical conditions.Our infrared absorption data were collected from thin fluid films(thickness less than~2μm)formed by pressing the prepared solutions in a Microcompression Cell with two diamond-II plates.The data show that both the O-H stretching mode and the O-H bending mode can be used as internal standards to determine the carbonate concentrations.Since the IR signals of the C-O antisymmetric stretching vibration of the CO32ion,and the O-H stretching and bending vibrations from our thin films are very strong,their relative IR absorbance intensity,if well calibrated,can be used to investigate the micron-sized carbonate-bearing aqueous fluid inclusions.This study establishes the first calibration of this kind,which may have some applications.Additionally,our spectroscopic data suggest that as the K_(2)CO_(3)concentration increases the aqueous solution forms more large water molecule clusters via more intense hydrogen-bonding.This process may significantly alter the physical and chemical behavior of the fluids.展开更多
Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physic...Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.展开更多
The quartz crystal microbalance(QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Contr...The quartz crystal microbalance(QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control of the temperature effect is one of the keys when using the QCM for high precision measurements. Based on the Sauerbrey's and Kanazawa's theories, we proposed a method for enhancing the accuracy of the QCM measurement, which takes into account not only the thermal variations of viscosity and density but also the thermal behavior of the QCM resonator. We presented an improved Sauerbrey equation that can be used to effectively compensate the drift of the QCM resonator. These results will play a significant role when applying the QCM at the room temperature.展开更多
The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as...The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as benzene, from aqueous solutions was carried out using the separation factor and permeation flux as the evaluating parameters. The effects of the CMS types and structures, feed concentrations on the pervaporation performance were preliminarily investigated.展开更多
For aqueous solutions with freezable bound water, vitrification and recrystallization are mingled, which brings difficulty to application and misleads the interpretation of relevant experiments. Here, we report a quan...For aqueous solutions with freezable bound water, vitrification and recrystallization are mingled, which brings difficulty to application and misleads the interpretation of relevant experiments. Here, we report a quantification scheme for the freezable bound water based on the water-content dependence of glass transition temperature, by which also the concentration range for the solutions that may undergo recrystallization finds a clear definition. Furthermore, we find that depending on the amount of the freezable bound water, different temperature protocols should be devised to achieve a complete recrystallization. Our results may be helpful for understanding the dynamics of supercooled aqueous solutions and for improving their manipulation in various industries.展开更多
Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is...Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.展开更多
We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively...We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.展开更多
Perovskite nanocrystals (NCs), which have emerged as a new class of phosphors with superb luminescence properties and bandgaps that can be easily tuned using chemical methods, have generated tremendous interest for ...Perovskite nanocrystals (NCs), which have emerged as a new class of phosphors with superb luminescence properties and bandgaps that can be easily tuned using chemical methods, have generated tremendous interest for a wide variety of applications where colloidal quantum dots have been very successful as carrier sources. In this study, self-assembled films of CsPbBr3 NCs were produced via drop casting of colloidal NCs onto glassy carbon electrodes (GCEs) to form an NC film-modified electrode. The possible fabrication process of the CsPbBr3 NCs films was discussed. We further studied the anodic electrochemiluminescence (ECL) behavior of the perovskite CsPbBr3 NCs film using cyclic voltammetry with tripropylamine (TPA) as a coreactant, and a possible ECL mechanism was proposed. Briefly, TPA was oxidized to produce strongly reducing radical spedes, which can react with electrochemically oxidized CsPbBr3 NCs to generate excited CsPbBr3 NCs* capable of light emission. The relative stability of the ECL emission of the CsPbBr3 NC films under aqueous conditions was also investigated, and it was found that they showed operational stability over the first three hours, indicating suitable reliability for application as sensing materials. The results suggested that semiconducting perovskite NCs have great potential for application in the ECL field.展开更多
In this work,an air-blast atomizing column was used to study the CO2 capture performance with aqueous MEA(mono-ethanol-amine)and Na OH solutions.The effects of gas flow rate,the liquid to gas ratio(L/G),the CO2 concen...In this work,an air-blast atomizing column was used to study the CO2 capture performance with aqueous MEA(mono-ethanol-amine)and Na OH solutions.The effects of gas flow rate,the liquid to gas ratio(L/G),the CO2 concentration on the CO2 removal efficiency(η)and the volumetric overall mass transfer coefficient(KGav)were investigated.The air-blast atomizing column was also compared with the pressure spray tower on the studies of the CO2 capture performance.For the aqueous MEA and Na OH solutions,the experimental results show that theηdecreases with increasing gas flow rate and CO2 concentration while it increases with increasing L/G.The effects on KGavare more complicated than those forη.When the CO2 concentration is low(3 vol%),KGavincreases with increasing gas flow rate while decreases with increasing L/G.However,when the CO2 concentration is high(9.5 vol%),as the gas flow rate and L/G increases,KGavincreases first and then decreases.The aqueous MEA solution achieves higherηand KGavthan the aqueous Na OH solution.The air-blast atomizing column shows a good performance on CO2 capture.展开更多
The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. ...The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. It was found that the separation results for aliphatic alcohols, amines and aldehydes are satisfactory, the solute rejection (R-a) and the volume fluxes of solutions (J(V)) for 1000 ppm ethanol, ethylamine and ethyl aldehyde are 66.2%, 61.0%, 84.0% and 0.90 x 10(-6), 0.35 x 10(-6), 0.40 X 10(-6) m(3)/m(2) . s, respectively, at 5.0 MPa and 30 degrees C. R-a increased with increasing molecular weights of alcohols, amines and aldehydes, and the R-a for n-amyl alcohol, n-butylamine and n-butyl aldehyde reached 94.3%, 88.6% and 96.0%, respectively. Satisfactory separation results (R-a > 70%) for ketones, esters, phenols and polyols have been obtained with the PAA/PSF composite membrane. The effect of operating pressure on the properties of reverse osmosis has also been investigated. Analysis of experimental data with Spiegler-Kedem's transport model has been carried out and the membrane constants such as reflection coefficient sigma, solute and hydraulic permeabilities omega and L-p for several organic solutes have been obtained.展开更多
A new type of rubidium ion-imprinted polymer has been synthesized by the surface-imprinting technique using methacrylic acid as the functional monomer,the rubidium ion as the template,methanol as the solvent,and silic...A new type of rubidium ion-imprinted polymer has been synthesized by the surface-imprinting technique using methacrylic acid as the functional monomer,the rubidium ion as the template,methanol as the solvent,and silica as a carrier.Ethylene glycol dimethacrylate and 2,2-azobisisobutyronitrile were used as acrosslinker and an initiator,respectively.In addition,based on the macrocyclic effect of crown ethers,the 18-crown-6 ligand was introduced as a ligand to fix the template ions better.Scanning electron microscopy,zeta-potential analysis,Fourier transform infrared spectroscopy,thermogravimetric analysis,and X-ray photoelectron spectroscopy were performed to characterize the ion-imprinted polymer.The effects of the preparation and adsorption conditions on the adsorption performance of the rubidium ion-imprinted polymer were investigated.The results indicated that the rubidium ion-imprinted polymer has high selectivity and faster kinetics than other adsorbents,with an equilibrium adsorption capacity of 200.19 mg·g^(-1)at 298 K within 25 min.The sorption isotherm was well described by the Freundlich isotherm model,while the adsorption kinetics fitted the pseudo-second-order kinetic model.Consecutive adsorption-desorption experiments showed that the ion-imprinted polymer had good chemical stability and reusability.展开更多
To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imid...To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imidazolate framework(ZIF-67)polyhedrons,which are used as precursors to prepare cobalt selenide/carbon composites with different crystal phases(Co_(0.85)Se,CoSe_2).When evaluated as anode material for lithium ion batteries,Co_(0.85)Se/C composites deliver a reversible capacity of 758.7 m A·h·g^(-1)with a capacity retention rate of 90.5%at 1.0 A·g^(-1)after 500 cycles,and the superior rate capability is 620 m A·h·g^(-1)at 2.0 A·g^(-1).The addition of KOH accelerates the production of ZIF-67 crystals by boosting deprotonation of dimethylimidazole,resulting in rapid growth and structures transition from two-dimensional to three-dimensional of ZIF-67 in aqueous solution,which greatly promotes the application of MOFs in the field of energy storage and conversion.展开更多
A novel high-yield Schiff base was designed and synthesized as an anion receptor that specifically select HSO3 anions in aqueous solutions of H20/DMSO(15:85, volume ratio), which can be detected via colorimetry und...A novel high-yield Schiff base was designed and synthesized as an anion receptor that specifically select HSO3 anions in aqueous solutions of H20/DMSO(15:85, volume ratio), which can be detected via colorimetry under direct visualization. The sensor exhibited different results for other anions, such as F, CI, Br, I-, H2PO4-, AcO-, HSO4 and C104. The changes in the UV-Vis spectra also show the specific recognition of HSO3 , rather than similar anions H2PO4- and HSO4- in the same aqueous solution. The detection limit of HSO3- was 1×10-6 mol/L.展开更多
All-atom molecular dynamics (MD) simulations and chemical shifts were used to study interactions and structures in the glycine-water system. Radial distribution functions and the hydrogen-bond network were applied i...All-atom molecular dynamics (MD) simulations and chemical shifts were used to study interactions and structures in the glycine-water system. Radial distribution functions and the hydrogen-bond network were applied in MD simulations. Aggregates in the aqueous glycine solution could be classified into different regions by analysis of the hydrogen-bonding network. Temperature-dependent NMR spectra and the viscosity of glycine in aqueous solutions were measured to compare with the results of MD simulations. The variation tendencies of the hydrogen atom chemical shifts and viscosity with concentration of glycine agree with the statistical results of hydrogen bonds in the MD simulations.展开更多
Ozone(O_(3)) generated by a dielectric barrier discharge(DBD) is widely used in various industrial processes. In this study, NaCl aqueous solution was used as a novel electric power transmission electrode in a DBD rea...Ozone(O_(3)) generated by a dielectric barrier discharge(DBD) is widely used in various industrial processes. In this study, NaCl aqueous solution was used as a novel electric power transmission electrode in a DBD reactor(instead of a traditional metal electrode) for highly efficient ozone generation. The results demonstrated that a high O_(3) yield of 242 g k Wh^(-1) with a concentration of 14.6 g m^(-3)O_(3) was achieved. The power transmission mechanism works because NaCl aqueous solution behaves as a capacitor when an alternating pulse voltage below 8 k Hz is used.Compared with the resistance of the discharge barrier and discharge space, the resistance of NaCl aqueous solution can be ignored, which ensures that O_(3) is generated efficiently. It is expected that O_(3) generation using NaCl aqueous solution as a novel electrode in a DBD reactor could be an alternative technology with good application prospects.展开更多
We utilize molecular dynamics simulations to investigate the microstructures of ions and polyelectrolytes in aqueous solutions under external electric fields.By focusing on the multi-body interactions between ionic co...We utilize molecular dynamics simulations to investigate the microstructures of ions and polyelectrolytes in aqueous solutions under external electric fields.By focusing on the multi-body interactions between ionic components and H_(2)O molecules,as well as their responses to the external electric fields,we clarify several nontrivial molecular features of the ionic and polyelectrolyte solutions,such as the solvations of cations and anions,clustering of the ions,and dispersions/aggregations of polyelectrolyte chains,as well as the corresponding responses of H_(2)O molecules in these contexts.Our simulations illustrate the variations in structures of ionic solutions caused by reversing the charge sign of the ions,and elucidate the disparity in structures between anionic and cationic polyelectrolyte solutions in the presence of the external electric fields.This work clarifies the mechanism for the alternations in complex multi-body interactions in aqueous solutions caused by the application electric field,which can contribute to the fundamental understanding of the physical and chemical natures of ion-containing and charged polymeric systems.展开更多
基金supported by the Key Area Research&Development Program of Guangdong Province(2020B0101070001)the National Natural Science Foundation of China(21978053,51508547)。
文摘Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.
基金Supported by the National Science Fund for Outstanding Young Scholars under Grant No 11422542the Key Research Program of Chinese Academy of Sciences under Grant No KJZD-EW-M03,KIPCAS+1 种基金the Shanghai Supercomputer Center of Chinathe High Performance Computing Center of Shanghai University
文摘How to determine accurately the association states of solutes in aqueous systems is of fundamental importance in a variety of chemical, physical, and biological processes, We apply four widely used criteria to analyze the dynamic association processes of solutes, e.g., amphiphilic molecules, and to find the inappropriate selections of representative sites on solutes in these criteria may bring about appreciable influence on the estimation of dynamic association behaviors such as unrealistic packing radii and even misleading packing structures. It would be better to select dynamically representative sites on solute molecules based on the characteristic of solute associations. Our detailed discussions give a guide on how to determine an appropriate criterion to accurately analyze the association behaviors of solute molecules in aqueous solutions.
文摘The adsorption of decylmethylsulfoxide(DEMS)onto carbon black and the effects of temperature,salt(NaCl)and acid (HCl)have been measured.Typical two plateaux type adsorption isotherms were obtained.Applying the two step model of surfactant adsorption on solid/liquld interface and the general adsorption isotherm equation[9]the experimental results were interpreted qualitatively and quantitatively.
基金supported by the National Natural Science Foundation of China (40673043 and 20576073)the Program for New Century Excellent Talents in University of Ministry of Education of China (NCET-06-0088)
文摘Ionic liquids (ILs) have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydrate formation. For illustration, the dilute aqueous solutions with concentrations of ILs ranging from 2× 10^-3 mol% to 2×10^-1 mol% were concentrated. The results show that the separation efficiency is very impressive and that the new method is applicable to aqueous solutions of both hydrophobic and hydrophilic ILs. Compared to the literature separation method based on the supercritical CO2, the new method is applicable to lower concentrations, and more importantly, its operation condition is mild.
基金the DREAM project of MOST,China(Grant No.2016YFC0600408)the Strategic Priority Research Program(B)of Chinese Academy of Sciences(Grant No.XDB18000000)the Program of the National Mineral Rock and Fossil Specimens Resource Center from MOST,China.
文摘Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with the size down to<1μm sometimes),and record critical physical-chemical signals for the formations of their host minerals.Spectroscopic methods like Raman spectroscopy and infrared spectroscopy have been proposed as effective methods to quantify the carbonate concentrations of these fluid inclusions.Although they have some great technical advantages over the conventional microthermometry method,there are still some technical difficulties to overcome before they can be routinely used to solve relevant geological problems.The typical limitations include their interlaboratory difference and poor performance on micro fluid inclusions.This study prepared standard ion-distilled water and K_(2)CO_(3)aqueous solutions at different molarities(from 0.5 to 5.5 mol/L),measured densities,collected Raman and infrared spectra,and explored correlations between the K_(2)CO_(3)molarity and the spectroscopic features at ambient P-T conditions.The result confirms that the Raman O-H stretching mode can be used as an internal standard to determine the carbonate concentrations despite some significant differences among the correlations,established in different laboratories,between the relative Raman intensity of the C-O symmetric stretching mode and that of the O-H stretching mode.It further reveals that the interlaboratory difference can be readily removed by performing one high-quality calibration experiment,provided that later quantifying analyses are conducted using the same Raman spectrometer with the same analytical conditions.Our infrared absorption data were collected from thin fluid films(thickness less than~2μm)formed by pressing the prepared solutions in a Microcompression Cell with two diamond-II plates.The data show that both the O-H stretching mode and the O-H bending mode can be used as internal standards to determine the carbonate concentrations.Since the IR signals of the C-O antisymmetric stretching vibration of the CO32ion,and the O-H stretching and bending vibrations from our thin films are very strong,their relative IR absorbance intensity,if well calibrated,can be used to investigate the micron-sized carbonate-bearing aqueous fluid inclusions.This study establishes the first calibration of this kind,which may have some applications.Additionally,our spectroscopic data suggest that as the K_(2)CO_(3)concentration increases the aqueous solution forms more large water molecule clusters via more intense hydrogen-bonding.This process may significantly alter the physical and chemical behavior of the fluids.
基金financially supported by grants from the National Natural Science Foundation of China(No.31500493)the Liaoning Educational Common Scientific Research Project(No.L2015044)+1 种基金the Liaoning Natural Science Foundation(No.2015020576)the Open Foundation of the Key Lab of Pulp and Paper Science & Technology,and Ministry of Education(Shandong Province),Qilu University of Technology(No.08031338)
文摘Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.
基金supported by the National Natural Science Foundation of China(Grant No.61672094)
文摘The quartz crystal microbalance(QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control of the temperature effect is one of the keys when using the QCM for high precision measurements. Based on the Sauerbrey's and Kanazawa's theories, we proposed a method for enhancing the accuracy of the QCM measurement, which takes into account not only the thermal variations of viscosity and density but also the thermal behavior of the QCM resonator. We presented an improved Sauerbrey equation that can be used to effectively compensate the drift of the QCM resonator. These results will play a significant role when applying the QCM at the room temperature.
文摘The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as benzene, from aqueous solutions was carried out using the separation factor and permeation flux as the evaluating parameters. The effects of the CMS types and structures, feed concentrations on the pervaporation performance were preliminarily investigated.
基金Project supported by the Knowledge Innovation Project of Chinese Academy of Sciences on Water Science Research(Grant No.KJZD-EW-M03)the National Natural Science Foundation of China(Grant Nos.11474325 and 11290161)
文摘For aqueous solutions with freezable bound water, vitrification and recrystallization are mingled, which brings difficulty to application and misleads the interpretation of relevant experiments. Here, we report a quantification scheme for the freezable bound water based on the water-content dependence of glass transition temperature, by which also the concentration range for the solutions that may undergo recrystallization finds a clear definition. Furthermore, we find that depending on the amount of the freezable bound water, different temperature protocols should be devised to achieve a complete recrystallization. Our results may be helpful for understanding the dynamics of supercooled aqueous solutions and for improving their manipulation in various industries.
基金supported by the National Natural Science Foundation of China(No.21776264).
文摘Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11974385 and 91956101).
文摘We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.
基金This research was financially supported by the National Natural Science Foundation of China (No. 21675133), the Marine high-tech industry development projects of Fujian Province (No. 2015-19). We thank Professor John Hodgkiss of the City University of Hong Kong for polishing the English.
文摘Perovskite nanocrystals (NCs), which have emerged as a new class of phosphors with superb luminescence properties and bandgaps that can be easily tuned using chemical methods, have generated tremendous interest for a wide variety of applications where colloidal quantum dots have been very successful as carrier sources. In this study, self-assembled films of CsPbBr3 NCs were produced via drop casting of colloidal NCs onto glassy carbon electrodes (GCEs) to form an NC film-modified electrode. The possible fabrication process of the CsPbBr3 NCs films was discussed. We further studied the anodic electrochemiluminescence (ECL) behavior of the perovskite CsPbBr3 NCs film using cyclic voltammetry with tripropylamine (TPA) as a coreactant, and a possible ECL mechanism was proposed. Briefly, TPA was oxidized to produce strongly reducing radical spedes, which can react with electrochemically oxidized CsPbBr3 NCs to generate excited CsPbBr3 NCs* capable of light emission. The relative stability of the ECL emission of the CsPbBr3 NC films under aqueous conditions was also investigated, and it was found that they showed operational stability over the first three hours, indicating suitable reliability for application as sensing materials. The results suggested that semiconducting perovskite NCs have great potential for application in the ECL field.
基金Supported by the National Natural Science Foundation of China(21729601,21776123)the Doctoral Program of Higher Education(20133221110001)+1 种基金the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Kempe Foundations,and Swedish Energy Agency(P40548-1).
文摘In this work,an air-blast atomizing column was used to study the CO2 capture performance with aqueous MEA(mono-ethanol-amine)and Na OH solutions.The effects of gas flow rate,the liquid to gas ratio(L/G),the CO2 concentration on the CO2 removal efficiency(η)and the volumetric overall mass transfer coefficient(KGav)were investigated.The air-blast atomizing column was also compared with the pressure spray tower on the studies of the CO2 capture performance.For the aqueous MEA and Na OH solutions,the experimental results show that theηdecreases with increasing gas flow rate and CO2 concentration while it increases with increasing L/G.The effects on KGavare more complicated than those forη.When the CO2 concentration is low(3 vol%),KGavincreases with increasing gas flow rate while decreases with increasing L/G.However,when the CO2 concentration is high(9.5 vol%),as the gas flow rate and L/G increases,KGavincreases first and then decreases.The aqueous MEA solution achieves higherηand KGavthan the aqueous Na OH solution.The air-blast atomizing column shows a good performance on CO2 capture.
文摘The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. It was found that the separation results for aliphatic alcohols, amines and aldehydes are satisfactory, the solute rejection (R-a) and the volume fluxes of solutions (J(V)) for 1000 ppm ethanol, ethylamine and ethyl aldehyde are 66.2%, 61.0%, 84.0% and 0.90 x 10(-6), 0.35 x 10(-6), 0.40 X 10(-6) m(3)/m(2) . s, respectively, at 5.0 MPa and 30 degrees C. R-a increased with increasing molecular weights of alcohols, amines and aldehydes, and the R-a for n-amyl alcohol, n-butylamine and n-butyl aldehyde reached 94.3%, 88.6% and 96.0%, respectively. Satisfactory separation results (R-a > 70%) for ketones, esters, phenols and polyols have been obtained with the PAA/PSF composite membrane. The effect of operating pressure on the properties of reverse osmosis has also been investigated. Analysis of experimental data with Spiegler-Kedem's transport model has been carried out and the membrane constants such as reflection coefficient sigma, solute and hydraulic permeabilities omega and L-p for several organic solutes have been obtained.
基金supported by the National Natural Science Foundation of China(22125802 and 22078010)Beijing Natural Science Foundation(2222017)Big Science Project from BUCT(XK180301)。
文摘A new type of rubidium ion-imprinted polymer has been synthesized by the surface-imprinting technique using methacrylic acid as the functional monomer,the rubidium ion as the template,methanol as the solvent,and silica as a carrier.Ethylene glycol dimethacrylate and 2,2-azobisisobutyronitrile were used as acrosslinker and an initiator,respectively.In addition,based on the macrocyclic effect of crown ethers,the 18-crown-6 ligand was introduced as a ligand to fix the template ions better.Scanning electron microscopy,zeta-potential analysis,Fourier transform infrared spectroscopy,thermogravimetric analysis,and X-ray photoelectron spectroscopy were performed to characterize the ion-imprinted polymer.The effects of the preparation and adsorption conditions on the adsorption performance of the rubidium ion-imprinted polymer were investigated.The results indicated that the rubidium ion-imprinted polymer has high selectivity and faster kinetics than other adsorbents,with an equilibrium adsorption capacity of 200.19 mg·g^(-1)at 298 K within 25 min.The sorption isotherm was well described by the Freundlich isotherm model,while the adsorption kinetics fitted the pseudo-second-order kinetic model.Consecutive adsorption-desorption experiments showed that the ion-imprinted polymer had good chemical stability and reusability.
基金financially supported by the National Key Research and Development Program of China (2017YFA0208200)the National Natural Science Foundation of China (52102100,22022505 and 21872069)+4 种基金the Natural Science Foundation of Jiangsu Province (BK20181469)Guangdong Basic and Applied Basic Research Foundation (2020A1515110035)the Fundamental Research Funds for the Central Universities (0205-14380266,0205-14380272)the Scientific and Technological Innovation Special Fund for Carbon Peak and Carbon Neutrality of Jiangsu Province (BK20220008)the 2021 Suzhou Gusu Leading Talents of Science and Technology Innovation and Entrepreneurship in Wujiang District。
文摘To solve the environmental pollution and low yield during the sythesis of zeolitic imidazolate frameworks(ZIFs)and their derived materials,a KOH-assisted aqueous strategy is proposed to synthesize cobalt zeolitic imidazolate framework(ZIF-67)polyhedrons,which are used as precursors to prepare cobalt selenide/carbon composites with different crystal phases(Co_(0.85)Se,CoSe_2).When evaluated as anode material for lithium ion batteries,Co_(0.85)Se/C composites deliver a reversible capacity of 758.7 m A·h·g^(-1)with a capacity retention rate of 90.5%at 1.0 A·g^(-1)after 500 cycles,and the superior rate capability is 620 m A·h·g^(-1)at 2.0 A·g^(-1).The addition of KOH accelerates the production of ZIF-67 crystals by boosting deprotonation of dimethylimidazole,resulting in rapid growth and structures transition from two-dimensional to three-dimensional of ZIF-67 in aqueous solution,which greatly promotes the application of MOFs in the field of energy storage and conversion.
基金Supported by the National Natural Science Foundation of China(Nos.21064006, 21161018 ), the Natural Science Foundation of Gansu Province, Chain(No. 1010RJZA018) and the Program for Changjian Scholars and Innovative Research Team in Univer- sity of Minisry of Education of China(No.IRT 1177).
文摘A novel high-yield Schiff base was designed and synthesized as an anion receptor that specifically select HSO3 anions in aqueous solutions of H20/DMSO(15:85, volume ratio), which can be detected via colorimetry under direct visualization. The sensor exhibited different results for other anions, such as F, CI, Br, I-, H2PO4-, AcO-, HSO4 and C104. The changes in the UV-Vis spectra also show the specific recognition of HSO3 , rather than similar anions H2PO4- and HSO4- in the same aqueous solution. The detection limit of HSO3- was 1×10-6 mol/L.
基金Supported by the National Natural Science Foundation of China(No.20903026)the Talents Introduction Foundation for Universities of Guangdong Province(2011)Scientific Research Foundation of the Natural Science Foundation of Guangdong Province(No.S2011010002483)
文摘All-atom molecular dynamics (MD) simulations and chemical shifts were used to study interactions and structures in the glycine-water system. Radial distribution functions and the hydrogen-bond network were applied in MD simulations. Aggregates in the aqueous glycine solution could be classified into different regions by analysis of the hydrogen-bonding network. Temperature-dependent NMR spectra and the viscosity of glycine in aqueous solutions were measured to compare with the results of MD simulations. The variation tendencies of the hydrogen atom chemical shifts and viscosity with concentration of glycine agree with the statistical results of hydrogen bonds in the MD simulations.
基金supported by National Natural Science Foundation of China (Nos. 12075037 and 22206013)the Natural Science Foundation of Jiangsu Province (No. BK20210857)the Leading Innovative Talents Cultivation Project of Changzhou City (No. CQ20210083)。
文摘Ozone(O_(3)) generated by a dielectric barrier discharge(DBD) is widely used in various industrial processes. In this study, NaCl aqueous solution was used as a novel electric power transmission electrode in a DBD reactor(instead of a traditional metal electrode) for highly efficient ozone generation. The results demonstrated that a high O_(3) yield of 242 g k Wh^(-1) with a concentration of 14.6 g m^(-3)O_(3) was achieved. The power transmission mechanism works because NaCl aqueous solution behaves as a capacitor when an alternating pulse voltage below 8 k Hz is used.Compared with the resistance of the discharge barrier and discharge space, the resistance of NaCl aqueous solution can be ignored, which ensures that O_(3) is generated efficiently. It is expected that O_(3) generation using NaCl aqueous solution as a novel electrode in a DBD reactor could be an alternative technology with good application prospects.
基金supported by the Major Science and Technology Projects for Independent Innovation of China FAW Group Co., Ltd. (No. 20220301018GX)the National Natural Science Foundation of China (Nos. 9237210012, 22073094 and 21474109)+2 种基金the Science and Technology Development Program of Jilin Province (Nos. 20240602003RC and 20210402059GH)the State Key Laboratory of Molecular Engineering of Polymers (Fudan University) (No. K2023-08)the Program for Young Scholars in Regional Development of CAS
文摘We utilize molecular dynamics simulations to investigate the microstructures of ions and polyelectrolytes in aqueous solutions under external electric fields.By focusing on the multi-body interactions between ionic components and H_(2)O molecules,as well as their responses to the external electric fields,we clarify several nontrivial molecular features of the ionic and polyelectrolyte solutions,such as the solvations of cations and anions,clustering of the ions,and dispersions/aggregations of polyelectrolyte chains,as well as the corresponding responses of H_(2)O molecules in these contexts.Our simulations illustrate the variations in structures of ionic solutions caused by reversing the charge sign of the ions,and elucidate the disparity in structures between anionic and cationic polyelectrolyte solutions in the presence of the external electric fields.This work clarifies the mechanism for the alternations in complex multi-body interactions in aqueous solutions caused by the application electric field,which can contribute to the fundamental understanding of the physical and chemical natures of ion-containing and charged polymeric systems.