Modulating the Electrolyte Inner Solvation Structure via Low Polarity Co-solvent for Low-Temperature Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries are regarded as the promising candidates for large-scale energy storage systems owing to low cost and high safety;however,their applications are restricted by their poor low-temperature performance.Herein,a low-temperature electrolyte for low-temperature aqueous zinc-ion batteries is designed by introducing low-polarity diglyme into an aqueous solution of Zn(ClO_(4))_(2).The diglyme disrupts the hydrogenbonding network of water and lowers the freezing point of the electrolyte to-105℃.The designed electrolyte achieves ionic conductivity up to16.18 mS cm^(-1)at-45℃.The diglyme and ClO_(4)^(-)reconfigure the solvated structure of Zn^(2+),which is more favorable for the desolvation of Zn^(2+)at low temperatures.In addition,the diglyme effectively suppresses the dendrites,hydrogen evolution reaction,and by-products of the zinc anode,improving the cycle stability of the battery.At-20℃,a Zn‖Zn symmetrical cell is cycled for 5200 h at 1 mA cm^(-2)and 1 mA h cm^(-2),and a Zn‖polyaniline battery achieves an ultra-long cycle life of 10000 times.This study sheds light on the future design of electrolytes with high ionic conductivity and easy desolvation at low temperatures for rechargeable batteries.

Distribution and transformation behaviors of heavy metals during liquefaction process of sewage sludge in ethanol-water mixed solvents

Liquefaction of sewage sludge(SS)in ethanol-water cosolvents is a promising process for the preparation of bio-oil/biochar products.Effect of the combined use of ethanol and water on the distribution/transformation behaviors of heavy metals(HMs)contained in raw SS is a key issue on the safety and cleanness of above liquefaction process,which is explored in this study.The results show that pure ethanol facilitates the migration of HMs into biochar products.Pure water yields lower percentages of HMs in mobile/bioavailable speciation.Compared with sole solvent treatment,ethanol-water cosolvent causes a random/average effect on the distribution/transformation behaviors of HMs.After liquefaction of SS in pure water,the contamination degree of HMs is mitigated from high level(25.8(contamination factor))in raw SS to considerable grade(13.4)in biochar and the ecological risk is mitigated from moderate risk(164.5(risk index))to low risk(78.8).Liquefaction of SS in pure ethanol makes no difference to the pollution characteristics of HMs.The combined use of ethanol and water presents similar immobilization effects on HMs to pure water treatment.The contamination factor and risk index of HMs in biochars obtained in ethanol-water cosolvent treatment are 13.1-14.6(considerable grade)and 79.3-101.0(low risk),respectively.In order to further control the pollution of HMs,it is preferentially suggested to improve the liquefaction process of SS in ethanol-water mixed solvents by introducing conventional lignocellulosic/algal biomass,also known as co-liquefaction treatment.

Morphology Control of SrCO_3 Crystals using Complexons as Modifiers in the Ethanol-water mixtures

Using SrC12-6H2O and Na2CO3 as the main raw materials and adding different complexons as modifiers with simple co-precipitation method, SrCO3 crystals with distinct morphologies like spherical, bundle-like, overlapping plate-like, hexagonal star-like, dumbbell-like, etc. can be synthesized in the ethanol-water mixtures. The samples were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and Fourier transform infrared spectrograph （FT-IR）. The interrelated effect mechanism is presented in the end. Results show that the modifier carboxyl groups play a significant role in controlling the SrCO3 crystal morphologies, which can alter the crystal growth unit （Sr^2＋） supply mode and induce the crystal formation with the morphologies matching their spatial configurations.

Fluorescence spectrum characteristic of ethanol-water excimer and mechanism of resonance energy transfer

The steady-state fluorescence spectrum characteristic of ethanol-water excimer has been studied in this paper. By analysing the features of the sharp emission spectrum with fine structures in a shortwave band and the characteristics of the broad and featureless fluorescence peaks in the longwave band, one can conclude that the excimers are formed between the new ethanol-water cluster molecules in the excited state and the ground state through the interaction among different chromophores. The excitation spectra in the two fluorescence bands have been studied, and their emission mechanisms have been ascertained based on the energy transfer theory. Furthermore, the critical distance of the resonance energy transfer has been calculated.

Dispersion of ZnO Nanocrytals in Co-solvent and Its Application in Photovoltaic Material

To overcome the aggregation of nanocrystals in a blend of inorganic material with conjugated polymers to prepare photovoltaic material, we used a co-solvent blend of CHCl3 with MeOH at a certain volume fraction to disperse inorganic nanocrystals. The results show that when the volume fraction of MeOH is 50%, ZnO nanocrystals with an average diameter of 30 nm disperse well in the co-solvent solution. Its application in photovoltaic material was investigated in this work, and the photoluminescence（PL） spectra show that when ZnO was 50%（volume fraction） in solution and 25%（volume fraction） in film, the fluorescence quenching reached the maximum values 83.34% and 64.4%, respectively, indicating that electron could transfer from conjugated polymer to electron-acceptor ZnO effectively.

Ethanol-Water Near-Azeotropic Mixture Dehydration by Compound Starch-Based Adsorbent

Ethanol-water near-azeotropic mixture dehydration was investigated by formulated compound starchbased adsorbent(CSA), which consists of corn, sweet potato and foaming agent. The net retention time and separation factor of water over ethanol were measured by inverse gas chromatography(IGC). Results indicated that water has a longer net retention time than ethanol and that low temperature is beneficial to this dehydration process. Orthogonal test was conducted under different vapor feed flow rates, bed temperatures and bed heights, to obtain optimal fixed-bed dehydration condition. Dynamic saturated adsorbance was also studied. It was found that CSA has the same water adsorption capacity(0.15 g/g)as some commercial molecular sieves. Besides, this biosorptive dehydration process was found to be the most energy-efficient compared with other ethanol purification processes.

Influence of Co-Solvent on the Extraction Behaviour of Uranium and Thorium Nitrates with Organophosphorous Compounds

Supercritical Fluid Extraction (SFE) is emerging as a powerful technique in the extraction of metal ions. In the present study, the extraction of nitrates of uranium and thorium was carried out using supercritical carbon dioxide (Sc-CO2) modified with various organophosphorous compounds such as dialkylalkyl phosphonates, trialkyl phosphates and trialkyl phosphine oxides in the presence of co-solvents such as methanol, dichlormethane and n-hexane. The influence of ligand and co-solvent on the extraction of the metal nitrates was studied in detail. These studies have established that co-solvent plays an important role in the extraction as well as fractionation of uranium and thorium nitrates. Polar co-solvent, methanol provided faster extraction without fractionation whereas the non-polar solvent, e.g. n-hexane provided some fractionation of metal nitrates though the extraction kinetics was slower.

Effect of Co-solvent and Pressure on the Thermal Decomposition of 2,2′Azobis-(isobutyronitrile) in Supercritical CO_2

The thermal decomposition of 2, 2'-azobis (isobutyronitrile) (AIBN) in supercritical CO2 with cosolvent methanol or cyclohexane has been studied by using UV/Vis spectroscopic method at 335.15 K and at 12.0 MPa and 14.0 MPa. Both of the cosolvents can accelerate the decomposition rate, and the effect of methanol is more significant than that of the cyclohexane.

Supercritical Synthesis of Ethyl Esters via Transesterification from Waste Cooking Oil Using a Co-Solvent

Biofuels became more promising alternative to the fossil fuels because of the depletion of fossil resources, renewability, environmental benefits, and energy security. Ethanolysis of waste cooking oil with hexane as co-solvent was carried out for the production of fatty acid ethyl ester (FAEE). This process reduced the severity of process parameters with high purity biodiesel yield. Process variables such as co-solvent ratio, ethanol to oil molar ratio, reaction temperature and reaction time were optimized. The maximum biodiesel yield of 88% was obtained at ethanol/oil molar ratio of 40:1, co-solvent (hexane) to oil ratio of 0.2% (v/v), reaction temperature of 300°C in 20 min of reaction time. Fatty acid ethyl ester (biodiesel) samples produced from this process were measured and evaluated using GC-MS analytical instrument. Thermo gravimetric analysis (TGA) was also performed to examine the thermal stability of waste cooking oil, ethyl esters and fuel blends. Fuel properties of ethyl esters were determined and compared with the ASTM standards for biodiesel, regular diesel and ethyl esters from different feedstock.

Kinetic Study of Cementation of Copper on Zinc Metal in Ethanol-Water Mixtures

The cementation reaction of copper on zinc metal in solutions of different concentrations ofcopper sulphate, at 25℃, has been studied and it is found to be a first order reaction. Moreover,the rates of this reaction at 0.15 mol'L-1 copper sulphate solution have been measured in a varietyof ethanol-water media at temperatures from 20℃ to 40℃. The correlation between the masstransfer coefficient and the dielectric constant has been investigated. Also, the thermodynamicparameters of activation have been calculated. The isokinetic relationship reveals the existenceof compensation effect, where the solute-solvent interactions play an important role.

Enhancement of Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquid with DMSO Co-solvent

Caffeic acid phenethyl ester(CAPE) is a natural and rare ingredient with several biological activities, but its industrial production using lipase-catalyzed esterification of caffeic acid(CA) and 2-phenylethanol(PE) in ionic liquids(ILs) is hindered by low substrate concentrations and long reaction time. To set up a high-efficiency bioprocess for production of CAPE, a novel dimethyl sulfoxide(DMSO)–IL co-solvent system was established in this study.The 2%(by volume) DMSO–[Bmim][Tf2N] system was found to be the best medium with higher substrate solubility and conversion of CA. Under the optimum conditions, the substrate concentration of CA was raised 8-fold,the reaction time was reduced by half, and the conversion reached 96.23%. The kinetics follows a ping-pong bi-bi mechanism with inhibition by PE, with kinetic parameters as follows: Vmax= 0.89 mmol · min-1· g-1, Km,CA=42.9 mmol · L-1, Km,PE= 165.7 mmol · L-1, and Ki,PE= 146.2 mmol · L-1. The results suggest that the DMSO cosolvent effect has great potential to enhance the enzymatic synthesis efficiency of CAPE in ILs.

Effects of Water-Soluble Co-Solvent on Properties of W/O Pickering Emulsions

Effects of water-soluble co-solvents （WSCs）on the properties of water/oil Picketing emulsions were investigated. Picketing emulsions were prepared in the system of 1,2,4-trimethylbenzene （TMB）/hydrophobic sil- ica/water with varied concentrations of WSCs （ethanol, acetic acid and glycerin）. Mean droplet diameter distribu- tions of the obtained emulsions were studied to investigate the effects of WSCs types and concentrations. The results demonstrated that mean droplet diameter distributions decreased at first and then increased with the increase of WSC concentration. Moreover, the effect of WSC concentration on the phase inversion locus was further investi- gated. At the same time, infrared radiation （IR）spectrometer was used to investigate the mechanism. The results showed that the WSC attaching on hydrophobic silica changed the wettability of the particles, which facilitated the formation and phase inversion of the emulsion. The hydrogen bonds between the co-solvent groups attaching on the solid particles made a great effect on the droplet size of the emulsion and strengthened the interaction among emulsifiers. Overall, proper WSC was in favor of the stability of Picketing emulsion.

Identification of Best Model for Equilibrium Data of Ethanol-Water Mixture

Four empirical models are tested for fitting the T-y-x equilibrium data of ethanol-water mixture by minimizing the Root Mean Square （RMS） between equilibrium data and theoretical points. The total pressure of the correspondent data is 101.3 kPa. All models parameters are also identified. The study suggests that NRTL model fits the equilibrium data best with RMS = 0.4 %.

Optimization of Biodiesel Production from Waste Vegetable Oil Assisted by Co-Solvent and Microwave Using a Two-Step Process

The two-step catalyzing process for biodiesel production from waste vegetable oil was assisted by both co-solvent and microwave irradiation. Central composite design (CCD) was employed to optimize the reaction conditions. Optimal reaction conditions of the first step were alcohol to oil molar ratio of 9:1, catalyst (H2SO4) amount 1 wt%, reaction temperature 333 K, and reaction time 7.5 minutes;while for the second step, optimal reaction conditions were alcohol to oil molar ratio 12:1, catalyst (NaOH) amount 1 wt%, reaction temperature 333 K, and reaction time 2.0 minutes. The total reaction time was 9.5 min and the conversion rate of fatty acid methyl esters (FAMEs) achieved was 97.4%. The total reaction time was shorter than previous studies. Therefore, the co-solvent and microwave assisted two-step catalyzing process has a potential application in producing biodiesel from waste vegetable oil.

Design of Pilot Plant Packed Column for the Dehydration of Water from Ethanol-Water Mixtures

This use of biomass-based adsorbent has been explored for the column study of the adsorptive dehydration of water in ethanol-water mixtures. The column study was carried out using enzyme modified corn starch and the breakthrough curve parameters were used to design the packed bed column. The effect of flow rate on the breakthrough curves revealed that adsorption efficiency decreased with increased inflow rate. The empty bed contact time (τ) of the pilot plant packed column was 35.35 min while the breakthrough time is 40.78 min. 66.7% was the fraction of capacity left unused for the pilot plant from the design.

水相循环对乙醇-水体系液化蜈蚣草产油特性和砷富集影响

砷富集植物的生态友好处置是实现植物修复产业化发展的关键环节,对土壤重金属污染治理高质量发展起到了制约作用。该研究以蜈蚣草为原料,采用乙醇-水作为反应共溶剂体系,考察了乙醇占比和水相循环次数对蜈蚣草水热产油及重金属砷分布的影响。研究结果显示:在乙醇浓度60%、水相循环3次的条件下,蜈蚣草液化生物油产率最高可达51.08%,其热值为29.15 MJ/kg。生物油主要由酯(>80%)、酚、醇、酮、烃等组成。随水相循环次数的增加,生物油中的酯类和酚类物质增加,高沸点化合物会减少,生物油产率和能量回收率分别提高了58%和32.23%;经过水相循环液化后,超过80%的重金属砷主要分布在水相,且砷的浓度增加至215.05 mg/kg,该结果可为砷富集植物无害化后处置提供参考。因此,水相循环利用是砷富集植物液化处置制取高产率生物油与砷富集的有效途径,为富集植物生态友好处置提供了新的思路。

An effective'salt in dimethyl sulfoxide/water'electrolyte enables high-voltage supercapacitor operated at-50℃

Compared with organic electrolytes,aqueous electrolytes exhibit significantly higher ionic conductivity and possess inherent safety features,showcasing unique advantages in supercapacitors.However,challenges remain for low-salt aqueous electrolytes operating at high voltage and low temperature.Herein,we report a low-salt(0.87 m,m means mol kg^(-1))'salt in dimethyl sulfoxide/water'hybrid electrolyte with non-flammability via hybridizing aqueous electrolyte with an organic co-solvent of dimethyl sulfoxide(hydrogen bond acceptor).As a result,the 0.87 m hybrid electrolyte exhibits enhanced electrochemical stability,a freezing temperature below-50℃,and an outstanding ionic conductivity of 0.52mS cm~(-1)at-50℃.Dimethyl sulfoxide can anchor water molecules through intermolecular hydrogen bond interaction,effectively reinforcing the stability of water in the hybrid electrolyte.Furthermore,the interaction between dimethyl sulfoxide and water molecules diminishes the involvement of water in the generation of ordered ice crystals,finally facilitating the low-temperature performance of the hybrid electrolyte.When paired with the 0.87 m'salt in dimethyl sulfoxide/water'hybrid electrolyte,the symmetric supercapacitor presents a 2.0 V high operating voltage at 25℃,and can operate stably at-50℃.Importantly,the suppressed electrochemical reaction of water at-50℃further leads to the symmetric supercapacitor operated at a higher voltage of 2.6 V.This modification strategy opens an effective avenue to develop low-salt electrolytes for high-voltage and low-temperature aqueous supercapacitors.

互花米草在乙醇-水体系中直接液化制备生物油

生物质因其储量丰富、来源广泛、碳中和等优势被认为是最具有应用前景的生产替代燃料的原料。在容积50 m L的小型高温高压反应釜中,利用醇-水共溶剂直接液化互花米草制备生物油,考察反应温度、醇-水共溶剂中乙醇体积分数、液料比对液化产物分布的影响,分析了原料的热重特性及生物油的主要成分。结果表明:随着升温速率的增加,互花米草的热失重曲线(thermogravimetric,TG)和微分热重曲线(differential thermogravimetric,DTG)基本保持不变,但却发生了不同程度的横向移动,出现明显的滞后现象,这是由温度和时间共同作用的结果;正交优化操作条件为温度340℃、乙醇体积分数50%、液料比10 m L/g,此时生物油产率高达44.2%,而残渣率仅为12%;与单一溶剂相比,醇-水共溶剂对互花米草的液化具有明显的协同作用,在提高产油率的同时能够显著改善生物油的品质;生物油的气相色谱-质谱分析表明生物油是一种组分复杂的含氧有机混合物,包括酸类、酚类、酯类、呋喃等,主要成分为酚类和酯类,相对含量分别为29.62%和11.27%;乙醇能够与酸发生酯化反应生成酯类,而酚类主要来自原料中木质素的降解;以乙醇体积分数为50%的醇-水共溶剂作为液化介质时,生物油的能量回收率为76.5%,明显高于以水或乙醇作为单一溶剂时液化所得生物油的能量回收率,因而醇-水共溶剂是生物质直接液化中非常有前景的液化介质。

用乙醇调节水溶性聚酯乳液的黏度及其机理分析

在质量分数为30.0%的水溶性聚酯乳液中,添加少量乙醇溶剂代替水可极大降低乳液的黏度。随着乙醇含量的增加,乳液黏度先减小后增加;乙醇质量分数为1.0%~9.0%时水溶性聚酯乳液黏度较低,超过9.0%时黏度急剧增加。用激光粒径分析仪测定了乳液粒径和界面电位。结果表明：添加少量乙醇引起水溶性聚酯乳液黏度降低的原因是由于乙醇共溶剂不利于聚酯高分子链中磺酸基的离子化,Zeta电位下降,且使乳液胶粒溶胀,导致其粒径增加;当乙醇质量分数超过9.0%后,水溶性聚酯乳液粒径快速增加,聚酯乳液胶粒扩散层重叠,导致体系黏度急剧增加。

污泥液化生物炭对亚甲基蓝的吸附特性及机理

探讨污泥在乙醇-水混合溶剂中液化产生的生物炭的吸附潜力及其吸附机理(以亚甲基蓝(MB)废水为处理对象),结果表明:生物炭的吸附容量随着MB溶液起始pH值升高而升高,当pH超过8时,MB的碱性褪色开始显现.吸附温度的上升(30~60℃)对生物炭吸附容量的影响不明显.吸附容量总体上随着吸附时间的增加而上升(240min前),在240min后趋于稳定.吸附剂用量及初始MB浓度过高或过低都不利于生物炭的吸附,存在一个的临界点,分别是6mg和120mg/L.生物炭吸附MB的过程吻合准二级动力学方程(R^2=0.9994)和Langmuir方程(R^2=0.9831),且为自发吸热的过程,受物理吸附和化学吸附联合控制,具体的机理包括:离子交换、官能团络合、π-π吸附等.