Disordered Structure and Reversible Phase Transformation from K-Birnessite to Zn-Buserite Enable High-Performance Aqueous Zinc-lon Batteries

The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.

Inhibiting the phase transition of WO_(3)for highly stable aqueous electrochromic battery

Aqueous electrochromic battery(ECB)has shown intense potential for achieving energy storage and saving simultaneously.While tungsten oxide(WO_(3))is the most promising EC material for commercialization,the cycling stability of WO_(3)-based aqueous ECBs is currently unsatisfactory due to the repeated phase transition during the redox process and the corrosion by acidic electrolytes.Herein,we present a titanium-tungsten oxide alloy(Ti-WO_(3))with controllable morphology and crystal phase synthesized by a facile hot injection method to overcome the challenges.In contrast to conventional monoclinic WO_(3),the Ti-WO_(3)nanorods can stably maintain their cubic crystal phase during the redox reaction in an acidic electrolyte,thus leading to dramatically enhanced response speed and cycling stability,Specifically,when working in a well-matched hybrid Al^(3+)/Zn^(2+)aqueous electrolyte,our phasetransition-free cubic Ti-WO_(3)exhibits an ultra-high cycling stability(>20000 cycles),fast response speed(3,95 s/4,65 s for bleaching/coloring),as well as excellent discharge areal capacity of 214.5 mA h m^(-2),We further fabricate a fully complementa ry aqueous electrochromic device,for the first time,using a Ti-WO_(3)/Prussian blue device architecture.Remarkably,the complementary ECB shows>10000 stable operation cycles,attesting to the feasibility of our Ti-WO_(3)for practical applications.Our work validates the significance of inhibiting the phase transitions of WO_(3)during the electrochromic process for realizing highly cyclable aqueous ECB,which can possibly provide a generalized design guidance for other high-quality metallic oxides for electrochemical applications.

MEASUREMENT AND CORRELATION OF PARTITION COEFFICIENTS OF UROKINASE IN AQUEOUS TWO-PHASE PEG-POTASSIUM PHOSPHATE SYSTEM

Partition coefficients of Urokinase(UK)were measured in aqueous two-phase systems con-taining polyethylene glycol and potassium phosphate at 273.2K.Based on the Diamond-Hsu model,a modified expression was obtained for the correlation of enzyme partitioning in theabove-mentioned systems.Utilizing a modified form,the partitioning data of UK and heteroproteinwere correlated.The results show that the modified model is simple gives good precision.and will fa-cilitate engineering scale-up of aqueous two-phase systems for certain proteins purification.

Novel Vesicular Aqueous Two-Phase Systems

The interesting phenopmena of two aqueous phases coexisting in dilute aqueous solutions of sodium undecenoate-dodecyltrimethylammo brodride ndxture and sodium laurate-dodecyltrimethylammonium brondde mixture were investigated. Vesicles existing in both phases were shown by TEM images. The vesicles are dispersed in lower phase and flocculated in upper phase. Multilamellar structure of vesicles was found in the upper phase of sodium laurate-dodecyltrimethylammonium bromide system.

Vanadium oxide nanospheres encapsulated in N-doped carbon nanofibers with morphology and defect dual-engineering toward advanced aqueous zinc-ion batteries

Vanadium-based electrodes are regarded as attractive cathode materials in aqueous zinc ion batteries(ZIBs)caused by their high capacity and unique layered structure.However,it is extremely challenging to acquire high electrochemical performance owing to the limited electronic conductivity,sluggish ion kinetics,and severe volume expansion during the insertion/extraction process of Zn^(2+).Herein,a series of V_(2)O_(3)nanospheres embedded N-doped carbon nanofiber structures with various V_(2)O_(3)spherical morphologies(solid,core-shell,hollow)have been designed for the first time by an electrospinning technique followed thermal treatments.The N-doped carbon nanofibers not only improve the electrical conductivity and the structural stability,but also provides encapsulating shells to prevent the vanadium dissolution and aggregation of V_(2)O_(3)particles.Furthermore,the varied morphological structures of V_(2)O_(3)with abundant oxygen vacancies can alleviate the volume change and increase the Zn^(2+)pathway.Besides,the phase transition between V_(2)O_(3)and Zn_XV_(2)O_(5-m)·n H_(2)O in the cycling was also certified.As a result,the as-obtained composite delivers excellent long-term cycle stability and enhanced rate performance for coin cells,which is also confirmed through density functional theory(DFT)calculations.Even assembled into flexible ZIBs,the sample still exhibits superior electrochemical performance,which may afford new design concept for flexible cathode materials of ZIBs.

Effects of Hydrophobicity of Ethylene Oxide-Propylene Oxide Copolymers on Phase Diagrams of Aqueous Two-Phase Systems and Partition Behaviors of Cephalexin and 7-Aminodeacetoxicephalos-poranic Acid

A series of ethylene oxide (EO)-propylene oxide (PO) randomco-polymers (EOPO) were used to form aqueous two-phase systems (ATPS)with ammonium sulfate. Effects of EOPO's properties on the phaseseparation behaviors and on the partition of cephalexin and7-aminodesacetoxicephalosporanic acid (7-ADCA) in ATPS wereinvestigated. Both the molar mass and molar ratio of EO to PO of EOPOcould greatly influence partition behaviors of cephalexin and 7-ADCAas well as the binodal curve of ATPS.

Thermodynamic modeling and phase diagram prediction of salt lake brine systems.Ⅰ. Aqueous Mg^2+–Ca^2+–Cl^- binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment.Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution,the multi-temperature characteristics and predictability are still the goals of model development.In this study,a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements:(1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range;(2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients,the liquid parameters,which associated with Gibbs energy,enthalpy,and heat capacity contribution;and(3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range.Together the activity coefficient model,property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl2-CaCl2-H2 O binary and ternary systems,and it shows excellent agreement with the literature data for the ternary and binary systems.The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-idealitv system,and the ability to extrapolate the temperature.

Thermodynamic modeling and phase diagram prediction of salt lake brine systemsⅡ.Aqueous Li^(+)-Na^(+)-K^(+)-SO_(4)^(2-) and its subsystems

It is still a challenging task to accurately and temperature-continuously express the thermodynamic properties and phase equilibrium behaviors of the salt-lake brine with multi-component,multitemperature and high concentration.The essential subsystem of sulfate type brine,aqueous Li^(+)-Na^(+)-K^(+)-SO_(4)^(2-) and its subsystems across a temperature range from 250 K to 643 K are investigated with the improved comprehensive thermodynamic model.Liquid parameters(Δg_(IJ),Δh_(IJ),and ΔC_(p,IJ))associated with the contributions of Gibbs energy,enthalpy,and heat capacity to the binary interaction parameters,i.e.the temperature coefficients of eNRTL parameters formulated with a Gibbs Helmholtz expression,are determined via multi-objective optimization method.The solid constantsΔ_(f)G_(k)°^((298.15))andΔ_(f)H_(k)°^((298.15))of11 solid species occurred in the quaternary system are rebuilt from multi-temperature solubilities.The modeling results show the accurate representation of(1)solution properties and binary phase diagram at temperature ranges from eutectic points to 643 K;(2)isothermal phase diagrams for Li_(2)SO_(4)-Na_(2)SO_(4)-H_(2)O,Li_(2)SO_(4)-K_(2)SO_(4)-H_(2)O and Na_(2)SO_(4)-K_(2)SO_(4)-H_(2)O ternary systems.The predicted results of complete structure and polythermal phase diagram of ternary systems and the isothermal phase diagrams of quaternary system excellently match with the experimental data.

Experimental Study on Aqueous Phase Entrainment in a Mixer-settler with Double Stirring Mode

The mixer-settler is a core device of solvent extraction for separating rare earth elements. There are some adverse effects like high rare earth accumulation and poor production efficiency during industrial production. Current researches usually focus on changing the structure of the mixer-settler without making a breakthrough towards gravity clarification. In this paper, in order to improve the efficiency of clarification, a mixer-settler with double stirring mode was designed and manufactured by adding a stirring device in the settler after reducing the volume of the settler. The innovation of this research involves adopting the ultraviolet-visible spectrophotometer to investigate the quantity of aqueous phase entrainment at the settler outlet in order to measure the clarification degree. Experimental results show that the clarification effect with stirring is better than that without stirring. The clarification effect is ameliorated as the stirring speed increases. Generally, the clarification effect shows a best condition when the offset distance is 12.5 cm, making the phase entrainment reduced to less than 0.1%. When the clearance over the tank bottom is 7 cm and 10 cm, respectively, the quantity of aqueous phase entrainment is better than the case with a clearance of 4 cm. The results show that the stirring paddle close to the mixed phase zone can better promote the two-phase separation.

Metallic vanadium trioxide intercalated with phase transformation for advanced aqueous zinc-ion batteries

Aqueous zinc-ion batteries have broad application prospects due to the eco-friendliness,cost-economy and high safety.However,the scarcity of high-performance cathodes with outstanding rate capability and long lifespan has affected their development.Herein,we report a metallic vanadium trioxide material intercalated with phase transformation as cathode applied in aqueous zinc-ion batteries.It offers satisfactory electrochemical performances with a high specific capacity(435 mAh g^(-1) at 0.5 A g^(-1)),decent power density(5.23 kW kg^(-1))and desired energy density(331 Wh kg^(-1)),as well as good cyclability.The superior performance originates from the stable structure and fast Zn^(2+)diffusion,enabled by the pre-intercalation of Zn^(2+)and water molecules.

Stability and activity of carbon nanofiber-supported catalysts in the aqueous phase reforming of ethylene glycol

Nickel, cobalt, copper and platinum nanoparticles supported on carbon nano-fibers were evaluated with respect to their stability, catalytic activity and selectivity in the aqueous phase reforming of ethylene glycol （230 ℃, autogenous pressure, batch reactor）. The initial surface-specific activities for ethylene glycol reforming were in a similar range but decreased in the order of Pt （15.5 h-1 ） 〉Co（13.0 h 1 ） 〉Ni（5.2 h-1） while the Cu catalyst only showed low dehydrogenation activity. The hydrogen molar selectivity decreased in the order of Pt （53%）〉Co（21%）〉Ni （15%） as a result of the production of methane over the latter two catalysts. Over the Co catalyst acids were formed in the liquid phase while alcohols were formed over Ni and Pt. Due to the low pH of the reaction mixture, especially in the case of Co （as a result of the formed acids）, significant cobalt leaching occurs which resulted in a rapid deactivation of this catalyst. Investigations of the spent catalysts with various techniques showed that metal particle growth is responsible for the deactivation of the Pt and Ni catalysts. In addition, coking might also contribute to the deactivation of the Ni catalyst.

Mixed phase sodium manganese oxide as cathode for enhanced aqueous zinc-ion storage

Aqueous zinc-ion batteries have been regarded as a promising alternative to large-scale energy storage, due to associated low-cost, improved safety and environmental friendliness. However, a high-performance cathode material for both rate capability and specific capacity is still a challenge. One kind of the more promising candidates are sodium manganese oxide(NMO) materials, although they suffer from individual issues and need to be further improved. Herein, we present a novel mixed phase NMO material composed of nearly equal amounts of Na(0.55)Mn2O4 and Na(0.7)MnO(2.05). The structured configuration with particle size of 200–500 nm is found to be beneficial towards improving the ion diffusion rate during the charge/discharge process. Compared with Na(0.7)MnO(2.05) and Na(0.55)Mn2O4, the mixed phase NMO demonstrates an enhanced rate capability and excellent long-term cycling stability with a capacity retention of 83% after 800 cycles. More importantly, the system also delivers an impressive energy density and power density, as 378 W·h·kg^-1 at 68.7 W·kg^-1, or 172 W·h·kg^-1 at 1705 W·kg^-1. The superior electrochemical performance is ascribed to the fast Zn^2+ diffusion rate because of a large ratio of capacitive contribution(63.9% at 0.9 m V·s^-1). Thus, the mixed phase route provides a novel strategy to enhance electrochemical performance, enabling mixed phase NMO as very promising material towards large-scale energy-storage applications.

ITO nano-powders prepared by microwave-assisted co-precipitation in aqueous phase

By using microwave-assisted co-precipitation in aqueous phase, adding surface activation agent PEG-6000 into the mixture of InCl3 solution and SnCl4 solution, and dropping the ammonia solution with the density (volume ratio) of 1-0 to 1-4, ITO precursor was prepared at different reaction system temperatures of 35 ℃-85 ℃, then ITO nano-powder was obtained after it was calcinated at 800 ℃ for 1 h. The morphology of ITO nano-powder was characterized by SEM and its electrical conductivity was determined by conductivity meter. The effects of different temperatures and ammonia concentration in microwave-assisted reaction system on its morphology and electric conductivity were discussed. The experimental results indicate that with the dilution of the ammonia solution or the rise of reacting system temperature, the morphology of ITO particles is transformed from spherical to rod-like one with the decline of its electric conductivity. And the electric conductivity of ITO nano-powders with spherical morphology is higher than that of ITO nano-powders with rod-like morphology.

An alternate aqueous phase synthesis of the Pt3Co/C catalyst towards efficient oxygen reduction reaction

Carbon supported Pt-Co alloys are among the most promising electrocatalysts towards oxygen reduction reaction(ORR)for the application in low temperature fuel cells and beyond,thus their facile and green synthesis is highly demanded.Herein we initially report an alternate aqueous phase one-pot synthesis of such catalysts(containing nominally ca.20 wt.%Pt)based on dimethylamine borane(DMAB)reduction.The as-obtained electrocatalyst(denoted as Pt3Co/C-DMAB)is compared with the ones obtained by NaBH4 and N2H4·H2O reduction(denoted as Pt3Co/C-NaBH4 and Pt3Co/C-N2H4·H2O,respectively)as well as a commercial Pt/C,in terms of the structure and electrocatalytic property.It turns out that Pt3Co/C-DMAB exhibits the highest ORR performance among all the tested samples in an O2-saturated 0.1 mol/L HClO4,with the mass activity(specific activity)ca.4(6)times as large as that for Pt/C.After 10000 cycles of the accelerated degradation test,the half-wave potential for ORR on Pt3Co/C-DMAB decreases only by 4 mV,in contrast to 24 mV for that on Pt/C.Pt3Co/C-NaBH4 or Pt3Co/C-N2H4·H2O shows a specific activity comparable to that for Pt3Co/C-DMAB,but a mass activity similar to that for Pt/C.ICP-AES,TEM,XRD and XPS characterizations indicate that Pt3Co nanoparticles are well-dispersed and alloyed with a mean particle size of ca.3.4±0.4 nm,contributing to the prominent electrocatalytic performance of Pt3Co/C-DMAB.This simple aqueous synthetic route may provide an alternate opportunity for developing efficient practical electrocatalysts for ORR.

Phase Equilibria of the Aqueous Systems Containing Lithium and Carbonate Ions

1 Introduction Alkaline lakes are widely distributed in the area of the Qinghai-Tibet Plateau.Most of the salt lakes are famous for their high concentration of lithium,potassium,magnesium,boron(Ma,2000).In recent years,as a new energy material,lithium and its compounds are widely used in the new area,such as aerospace industry,nuclear

Renewable Hydrogen Produced from Different Renewable Feedstock by Aqueous-Phase Reforming Process

Aqueous phase reforming (APR) of biomass derived feedstock producing hydrogen was reviewed. The APR process was discussed based on different feedstock categories such as sugars, polyols and ethanol. The mechanism of APR was analyzed referring to different structures of feedstock. The reaction pathways of APR were investigated. The usage of catalysts should be judged by feedstock on the requirement including C-C bond cleavage, water-gas shift (WGS) reaction, and catalyst maintenance. The prospects were concluded based on the recent works from bimetallic catalysts and high efficient supports. Examples of significant challenges of reducing catalyst cost and increasing catalyst stability have been discussed. The modification and utilization of alkane selectivity of APR processes for liquid fuel production was also investigated.

Effect of initial nickel particle size on stability of nickel catalysts for aqueous phase reforming

The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.

Partition coefficient prediction of Baker's yeast invertase in aqueous two phase systems using hybrid group method data handling neural network

A hybrid GMDH neural network model has been developed in order to predict the partition coefficients of invertase from Baker's yeast. ATPS experiments were carried out changing the molar average mass of PEG(1500–6000 Da), p H(4.0–7.0), percentage of PEG(10.0–20.0 w/w), percentage of MgSO_4(8.0–16.0 w/w), percentage of the cell homogenate(10.0–20.0 w/w) and the percentage of MnSO_4(0–5.0 w/w) added as cosolute. The network evaluation was carried out comparing the partition coefficients obtained from the hybrid GMDH neural network with the experimental data using different statistical metrics. The hybrid GMDH neural network model showed better fitting(AARD = 32.752%) as well as good generalization capacity of the partition coefficients of the ATPS than the original GMDH network approach and a BPANN model. Therefore hybrid GMDH neural network model appears as a powerful tool for predicting partition coefficients during downstream processing of biomolecules.

Layered buserite Mg-Mn oxide cathode for aqueous rechargeable Mg-ion battery

Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor Mg^(2+)migration kinetics during the Mg^(2+)intercalation/extraction still hinders the progress of developing suitable cathode materials.Herein,a layered buserite Mg-Mn oxide(MMO)material with large interlayer space(~9.70A)and low-crystalline structure is studied as a high-performance cathode in ARMIBs.Compared with the counterpart,the Mg^(2+)migration kinetics of the MMO cathode can be enhanced by its unique structure(bigger interlayer spacing and low-crystalline structure).The layered buserite MMO as a high-performance ARMIBs cathode exhibits high Mg storage capacity(50 mAg^(-1):169.3 mAh g^(-1)),excellent rate capability(1000 mAg^(-1):98.3 mAh g^(-1)),and fast Mg^(2+)migration(an average diffusion coefficient:~4.21×10-^(10)cm^(2)s^(-1))in 0.5 M MgCl_(2)aqueous electrolyte.Moreover,the MMO-1//AC full battery achieved a high discharge capacity(100 mAg^(-1):111 mAh g^(-1)),and an ignored fading over 5000 cycles(1000 mAg^(-1)).Therefore,layered Mg-Mn oxide with large interlayer space may break a new path to develop the promising ARMIBs.

AQUEOUS PHASE RHODIUM HYDROFORMYLATION OF DODECENE－1 WITH SURFACE ACTIVE WATER－SOLUBLE PHOSPHINE

The surface active water-soluble phosphine, P[p-C6H4O(CH2CH2O)nH]3, n=4, is used to generate an squeous rhoditun catalyst for the hydroformylation of dodecene-1. Under I00℃, 5.0 MPa (CO/H2=1∶1 ), pH=6.5, and reachon time 4h, the conversion of dodecene-1 was 96.0%, the yield for aldehyde was 84.0%. and n/i =1.8. The catalyst can be reused for more than four times without any appreciable loss in activity and selechvity.