Hydrophobic CHA-ZIFs with a junctional trap between cha and d6r cages for adsorption of 2,3-butanediol in aqueous solution

The adsorption and separation of diols from dilute aqueous solution using hydrophobic materials is very challenging due to the strong diol-water hydrogen-bonding interactions. Herein, we screened hydrophobic zeolitic imidazolate frameworks(ZIFs) with chabazite(CHA) topology for separation of 2,3-butanediol(2,3-BDO) and 1,3-propanediol(1,3-PDO), which had junctional and hydrophobic traps matching the two end methyl groups of the 2,3-BDO molecule. Based on CHA-ZIFs with the same small-sized ligand 2-methylimidazole(mIm) and different large-sized ligand benzimidazole derivatives(RbIm),CHA-ZIFs with larger surface areas were obtained by the addition of excess small-sized ligand mIm in the synthesis process. We showed that all of the hydrophobic CHA-ZIFs preferentially adsorbed 2,3-BDO over 1,3-PDO by static batch adsorption and dynamic column adsorption experiments. But ZIF-301 and ZIF-300 with halogen groups exhibited better adsorptive separation performance for 2,3-BDO/1,3-PDO than ZIF-302 with methyl groups. For a typical ZIF-301, its adsorption capacity for 2,3-BDO was 116.4 mg·g^(-1)and selectivity for 2,3-BDO/1,3-PDO was 3.8 in dynamic column adsorption of the binary-component system(2,3-BDO/1,3-PDO: 50 g·L^(-1)/50 g·L^(-1)). Computational simulations revealed that 2,3-BDO preferentially adsorbed in a trap at the junction between the cha and d6r cages of CHA-ZIFs,meaning the strong host-guest interactions. Therefore, the hydrophobic CHA-ZIFs with a junctional trap were promising candidate materials for adsorbing 2,3-BDO, which also provided a new perspective for separating diols in dilute aqueous solutions.

Ligand-free Cs2PdBr6 perovskite microcrystals with narrow bandgap and high photoelectrochemical performance in aqueous solution

The exploration of efficient lead-free perovskite photoelectric active materials to develop high-performance photoelectrochemical(PEC)systems in aqueous solution is crucial to expand their PEC applications.Herein,we successfully constructed a high-performance PEC platform using ligand-free perovskite Cs2PdBr6 microcrystals(MCs)as the photoactive substance.The Cs2PdBr6 MCs showed narrow bandgap,wide absorption range,high electronic mobility and good stability in aqueous solutions.Particularly,the Cs2PdBr6 MCs exhibited an excellent photoresponse,the photocurrent density could reach as high as 98μA/cm^(2)under 10.18 mW/cm^(2)light irradiation in the absence of other electron acceptors.In addition of the extremely wide range of response wavelength,wide pH range and accelerated interfacial carrier transfer,the Cs2PdBr6 MCs demonstrated the significant potential of photocathode active material for applications in PEC sensors and optoelectronic devices.Therefore,this work indicates that Cs2PdBr6 MCs design is a highly efficient way to solve the intrinsic issues of perovskite material,predicting a promising strategy for high performance PEC application in aqueous ambience.

Removal of cadmium from aqueous solutions using red mud granulated with cement

A novel adsorbent was prepared from granular red mud mixed with cement and its potential to be a suitable adsorbent for the removal of cadmium ions from aqueous solutions was evaluated. The wet red mud was directly mixed up with cement at different mass fractions of 2%-8% and their properties were investigated. Based on the textural characteristics and strength, the granular red mud with 2% addition of cement maintaining for 6 d is identified to have better properties. The batch adsorption experiments for adsorption of Cd2+ ions from solution were performed at 30, 40 and 50 °C at different initial concentrations under the condition of constant pH of 6.5. The equilibrium adsorption was found to increase with the increase of temperature during the adsorption process. Langmuir adsorption isotherm model was found to match the experimental adsorption isotherm better. The kinetics of adsorption was modeled using a pseudo second order kinetic model and the model parameters were estimated.

Aqueous ammonia solution cooling absorption refrigeration driven by fishing boat diesel exhaust heat

A solution cooling absorption（SCA）approach is proposed to modify the aqueous ammonia absorption refrigerat-ion cycle using the strong solution from the absorber to cool the forepart of the absorption in the cycle for reclaiming some portion of absorption heat.As a consequence of raised temperature at the inlet,the strong solution partially boils at the outlet of the solution heat exchanger,and diminishes the thermal heat consumption of the heat source.The calculation results show that the coefficient of performance（COP）of this modified cycle is about 28.3% higher than that of the traditional cycle under typical conditions;while the required heat transfer area of the total heat exchangers of the cycle is somewhat less than that of the traditional one.The capacity of refrigeration with the new absorption cycle is more than doubled in contrast to the adsorption scheme with an identical configuration.It is sufficient to supply a fishing boat the chilling capacity for preservation of fishing products with the modified cycle chiller driven by its diesel engine exhaust.

A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in aqueous solutions and its applications in binary and ternary aqueous solutions

A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.

Preparation of Cu nanoparticles with ascorbic acid by aqueous solution reduction method

Cu nanoparticles were prepared by reducing Cu2＋ ions with ascorbic acid through aqueous solution reduction method. The effects of solution pH and average size of Cu2O particles on the preparation of Cu nanoparticles were investigated. Cu particles were prepared at pH 3, 5 or 7, with the smallest Cu particles obtained at pH 7. However, Cu particles could not be prepared at pH 9 or 11. The average size of Cu2O particles can affect that of Cu particles. Larger Cu2O particles result in larger Cu particles. In addition, experiments were conducted to explore the reaction process by measuring the X-ray diffraction （XRD） patterns of specimens collected at different time points during the reaction. It was found that Cu（OH）2 was initially formed as a precursor, followed by the formation of Cu2O, which was finally reduced to Cu particles.

Effects of reaction parameters on preparation of Cu nanoparticles via aqueous solution reduction method with NaBH_4

The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.

All-atom Molecular Dynamics Simulationsand NMR Spectroscopy Study on Interactions and Structures in N-Glycylglycine Aqueous Solution

All-atom molecular dynamics （MD） simulation and the NMR spectra are used to investigate the interactions in N-glycylglycine aqueous solution. Different types of atoms exhibit different capability in forming hydrogen bonds by the radial distribution function analysis. Some typical dominant aggregates are found in different types of hydrogen bonds by the statistical hydrogen-bonding network. Moreover, temperature-dependent NMR are used to compare with the results of the MD simulations. The chemical shifts of the three hydrogen atoms all decrease with the temperature increasing which reveals that the hydrogen bonds are dominant in the glycylglycine aqueous solution. And the NMR results show agreement with the MD simulations. All-atom MD simulations and NMR spectra are successful in revealing the structures and interactions in the N-glycylglycine-water mixtures.

Conformations of Carnosine in Aqueous Solutions by All-Atom Molecular Dynamics Simulations and 2D-NOSEY Spectrum

All-atom molecular simulations and two-dimensional nuclear overhauser effect spectrum have been used to study the conformations of carnosine in aqueous solution. Intramolecular distances, root-mean-square deviation, radius of gyration, and solvent-accessible surface are used to characterize the properties of the carnosine. Carnosine can shift between extended and folded states, but exists mostly in extended state in water. Its preference for extension in pure water has been proven by the 2D nuclear magnetic resonance （NMR） experiment. The NMR experimental results are consistent with the molecular dynamics simulations.

COSMO-RS prediction and experimental verification of 1,5-pentanediamine extraction from aqueous solution by ionic liquids

1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.

Separation of ionic liquids from dilute aqueous solutions using the method based on CO_2 hydrates

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.

One-pot degradation of cellulose into carbon dots and organic acids in its homogeneous aqueous solution

As the abundant biopolymer, cellulose can be used as a feedstock for chemicals and materials. Effective conversion of cellulose by simple processes is a key point. Degradation of cellulose in its homogeneous solution is attractive for the molecular chains are free and spread. Here,microcrystalline cellulose was first dissolved in aqueous solution of Na OH and urea, and then hydrothermal reaction was carried out at various temperature and time. Fluorescence carbon dots(CDs) were generated accompanied with six organic acids: oxalic acid, formic acid, malonic acid, lactic acid, acetic acid, and fumaric acid. The yields of all organic acids and CDs, and the fluorescence quantum yield(QY) of CDs were studied at different reaction conditions. It was found that the maximum yield of organic acids and CDs are 80.1% and 6.03%, respectively, and the highest QY of the CDs is 10.9%. Fluorescence studies reveal that the as-prepared CDs has efficient selectivity and sensitivity toward iron ions in acidic condition, indicating it is a potential fluorescent sensor to the detection of Fe3+. Importantly, it provides a panorama to summary the degradation routes of cellulose in its homogeneous aqueous solution with both organic molecules and CDs as products.

Adsorption of rubidium ion from aqueous solution by surface ion imprinted materials

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.

Alpha radiolysis of nitric acid aqueous solution irradiated by 238Pu source

Alpha radiolysis of nitric acid aqueous solution by a ^(238)Pu source is investigated experimentally and theoretically.The time dependence of the nitrous acid yield on dose rate,nitric acid concentration,and nitrate ion concentration is studied.A novel kinetic model for the α-radiolysis of nitric acid aqueous solution is established,by considering the direct and indirect effects.The simulation results agree well with the experimental data,indicating the validity of our model to treat the reaction paths for generation and consumption of nitrous acid.It is shown that the redox reactions involving Pu cannot be neglected in theα-radiolysis of the solution.The results provide a better understanding of the α-ray radiolysis of aqueous nitric acid.

Study of the Relationship Between New Ionic Interaction Parameters and Salt Solubility in Electrolyte Solutions Based on Molecular Dynamics Simulation

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.

Degradation of α-Naphthol by Plasma in Aqueous Solution

Degradation of α-naphthol induced by plasma in aqueous solution was investigated in different initial concentration with contact glow discharge electrolysis(CGDE). The results showed that the degradation of α-naphthol obeyed the first-rate law. Some of predominant products were analyzed by a high performance liquid chromatography (HPLC). A path of α-naphthol disappearance caused by plasma was proposed according to the detected intermediate products.

(Short communication) Degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution

To investigate the degradation of corrosion resistance of Zircaloy-4 in LiOHaqueous solution, SIMS (secondary ion mass spectrometry) analysis was performed to examine theprofiles of Li^+, K^+, and OH^- in oxide layers formed in the same concentration (0.1 mol/L) LiOHand KOH solutions. Even though the oxide layers have an equal thickness, the pene-tration depth ofK^+ is shallower than that of Li^+, and the penetration depth of OH^- corroded in KOH solution isalso shal-ower than that corroded in LiOH solution. It shows that the diffusion of OH^- into oxidelayer is accompanied by the corresponding cation. The difference of degradation effect of LiOH andKOH solutions on the corrosion resistance of Zircaloy-4 was discussed.

Volumetric and Transport Properties of Aqueous NaB（OH）4 Solutions

Density, pH, viscosity, conductivity and the Raman spectra of aqueous NaB（OH）4 solutions precisely measured as functions of concentration at different temperatures （293.15, 298.15, 303.15, 313.15 and 323.15 K） are presented. Polyborate distributions in aqueous NaB（OH）4 solution were calculated, covering all the concentration range, B（OH）4 is the most dominant species, other polyborate anions are less than 5.0%. The volumetric and the transport properties were discussed in detail, both of these properties indicate that B（OH）4 behaves as a struc- ture-disordered anion.

Correlation of ^1H NMR Chemical Shift for Aqueous Solutions by Statistical Associating Fluid Theory Association Model

1H NMR chemical shifts of binary aqueous mixtures of acylamide, alcohol, dimethyl sulphoxide (DMSO), and acetone are correlated by statistical associating fluid theory (SAFT) association model. The comparison between SAPT association model and Wilson equation shows that the former is better for dealing with aqueous solutions. Finally, the specialties of both models are discussed.

Removal of lead(Pb(Ⅱ))and zinc(Zn(Ⅱ))from aqueous solution using coal fly ash(CFA)as a dual-sites adsorbent

Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with unique properties.This work focused on the adsorption of Pb(Ⅱ)and Zn(Ⅱ)from binary system,a mixture containing two metal ion solutions present simultaneously,onto NaOH-modified CFA(MCFA).Several adsorption tests were conducted to evaluate the effect of several parameters,including pH and contact times.The experiment results indicated that chemical treatment of CFA with NaOH increased pore volume from 0.021 to 0.223 cm^3·g^(-1).In addition,it could also enhance the availability of functional groups on both minerals and unburned carbon,resulting in almost 100%Pb(Ⅱ)and 97%Zn(Ⅱ)adsorbed.The optimum pH for adsorption system was pH=3 and quasi-equilibrium occurred in 240 minutes.Equilibrium data from the experimental results were analyzed using Modified Extended Langmuir(MEL)and Competitive Adsorption Langmuir-Langmuir(CALL)isotherm models.The analysis results showed that the CALL isotherm model could better describe the Pb(Ⅱ)and Zn(Ⅱ)adsorption process onto MCFA in binary system compared with MEL isotherm model.