Metal-organic cage as fluorescent probe for LiPF_(6)in lithium batteries

Lithium hexafluorophosphate(LiPF_(6)),the most commonly used lithium battery electrolyte salt,is vulnerable to heat and humidity.Quantitative and qualitative determination the variation of LiPF_(6)have always relied on advanced equipment.Herein,we develop a fast,convenient,high-selective fluorescence detection method based on metal-organic cages(MOC),whose emission is enhanced by nearly 20 times in the presence of LiPF_(6)with good stability and photobleaching resistance.The fluorescent probe can also detect moisture in battery electrolyte.We propose and verify that the luminescence enhancement is due to the presence of hydrogen bond-induced enhanced emission effect in cages.Fluorescent excitation-emission matrix spectra and variable-temperature nuclear magnetic resonance spectroscopy are employed to clarify the role of hydrogen bonds in guest-loaded cages.Density functional theory(DFT)calculation is applied to simulate the structure of host-guest complexes and estimate the adsorption energy involved in the system.The precisely matched lock-and-key model paves a new way for designing and fabricating novel host structures,enabling specific recognition of other target compounds.

Solid-liquid phase equilibrium for the system ammonium polyphosphate-urea ammonium nitrate-potassium chloride-water at 273.2 K

Based on the dynamic method,a quaternary system of ammonium polyphosphate (APP)-urea ammonium nitrate (UAN,CO(NH_(2))_(2)-NH_(4)NO_(3))-potassium chloride (KCl)-H_(2)O and its subsystems (APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O and APP-KCl-H_(2)O) were systematically investigated at the temperature of 273.2 K.Each ternary phase diagram contains one invariant point and three crystallization regions.The crystallization regions are:(1)(NH_(4))_(3)HP_(2)O_(7),(NH_(4))_(4)P_(2)O_(7)and ((NH_(4))_(3)HP_(2)O_(7)+(NH_(4))_(4)P_(2)O_(7)) for APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O diagram;(2) KCl,KNO_(3)and(KCl+KNO_(3)) for KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O diagram and (3)(NH_(4))_(3)HP_(2)O_(7),KCl and((NH_(4))_(3)HP_(2)O_(7)+KCl) for APP-KCl-H_(2)O diagram.The quaternary phase diagram of APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-KCl-H_(2)O has no quaternary invariant point but includes four solid phase crystallization regions,i.e.,(NH_(4))_(3)HP_(2)O_(7),(NH_(4))_(4)P_(2)O_(7),KNO_(3)and KCl,in which the KNO_(3)region occupies the largest area.The maximum total nutrient content (N+P_(2)O_(5)+K_(2)O) existing as ionic forms in the APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,APP-KCl-H_(2)O and quaternary systems is 44.70%,32.86%,45.56%and 46.23%(mass),respectively,indicating that the maximum nutrient content can be reached using raw materials of the corresponding systems to prepare liquid fertilizer.In the quaternary system,the content of NH_(4)~+-N ascends with the increase of the total nutrient content,while the contents of NO_(3)^(-)-N and CO(NH_(2))_(2)-N increase with elevated total N.This work can help optimize the operating parameters for the production,storage and transportation of liquid fertilizers.

Mechanism and kinetics study on removal of Iron from phosphoric acid by cation exchange resin

Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m2·g-1 and 5.18 mmol·g-1, respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO3 H in resin. The removal process was studied as a function of temperature, H3 PO4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g-1 resin when the operating parameters were T = 50 ℃, H3 PO4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol-1. The overall reaction process was mainly controlled by pore diffusion.

The development road of ammonium phosphate fertilizer in China

Ammonium phosphate fertilizer is the compounds containing nitrogen and phosphorus that are usually produced through the neutralization reaction of phosphoric acid and ammonia.At present,there are a variety of products,such as slurry monoammonium phosphate(MAP),diammonium phosphate(DAP),industrial grade MAP,water soluble MAP,water soluble ammonium polyphosphate(APP)and so on.After more than 60 years of development,China’s ammonium phosphate fertilizer industry has experienced the road of from scratch and from weak to strong.The successful development of the slurry MAP technology ended the history that the high concentration phosphate fertilizer cannot be produced by using the medium and low grade phosphate ore.The continuous,stable and large-scale production of DAP plant provides sufficient guarantee for DAP products in China.The development of new ammonium phosphate fertilizer products,such as industrial grade MAP,water soluble MAP,water soluble APP,provides technical support for the transformation and upgrading of phosphorus chemical enterprises.In this paper,the production methods,the development history and the latest research progress of ammonium phosphate fertilizers were reviewed.

Leaching calcium from phosphogypsum desulfurization slag by using ammonium chloride solution: Thermodynamics and kinetics study

Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurization slag, which mainly contains two steps: leaching and carbonizing. In this work, we concentrated on the former, in which ammonium chloride aqueous solution was utilized as leaching agent to extract calcium from the slag, and conducted thermodynamics and kinetics study on it. Fact Sage software was employed to do thermodynamic and phase equilibrium diagram calculations. The influence of leaching conditions including agitation speed, initial concentration of leaching solution, reaction temperature, and liquid/solid ratio on the calcium leaching rate was discussed in detail by means of experiment optimal design. A kinetic model developed from the shrinking core model was given to describe the leaching process. The apparent kinetic activation energy(Ea) of the leaching reaction was calculated to be 10.58 kJ·mol^-1.

Solubility and solution thermodynamics of ammonium dihydrogen phosphate in the water–methanol system

The solubility of ammonium dihydrogen phosphate(MAP)in the water–methanol system is essential for antisolvent crystallization studies.To investigate the effect of methanol on the solubility of MAP in water,the solubility of MAP in the water–methanol system was determined by dynamic method and static equilibrium method at temperatures ranging from 293.2 to 343.2 K at atmospheric pressure.Results showed that the solubility of MAP increased with the increase of temperature and the increase of water mole fraction in the water–methanol system.The experimental solubility data were correlated with the modified Apelblat equation,the combined nearly ideal binary solvent/Redlich–Kister(CNIBS/R–K)model and the Jouyban–Acree model.The calculated results based on these three models were in very good agreement with the experimental data with the average relative deviations of 0.65%,0.97%,and 5.38%,respectively.Simultaneously,the thermodynamic properties of the MAP dissolution process in the water–methanol system,including Gibbs energy change,enthalpy,and entropy were obtained by the Van’t Hoff equation,which can be used to assess the crystallization process.

Structural model for the first wall W-based material in ITER project

The preparation, characterization, and test of the first wall materials designed to be used in the fusion reactor have remained challenging problems in the material science. This work uses the firstprinciples method as implemented in the CASTEP package to study the influ ences of the doped titanium carbide on the structural sta bility of the WTiC material. The calculated total energy and enthalpy have been used as criteria to judge the structural models built with consideration of symmetry. Our simulation indicates that the doped TiC tends to form its own domain up to the investigated nanoscale, which implies a possible phase separation. This result reveals the intrinsic reason for the composite nature of the WTiC material and provides an explanation for the experimen tally observed phase separation at the nanoscale. Our approach also sheds a light on explaining the enhancing effects of doped components on the durability, reliability, corrosion resistance, etc., in many special steels.

磷酸二氢铵-磷酸氢二铵-聚磷酸铵-水四元体系相平衡的实验与计算

利用Schreinemaker湿渣法,通过离子色谱和质量守恒方程联立得到各组分在饱和液相和湿渣相中的分布,从而得到25℃下磷酸二氢铵-磷酸氢二铵-聚磷酸铵-水四元空间相图,解释了聚磷酸铵水溶液结晶、沉淀的问题,对聚磷酸铵作为高效水溶肥料使用、储存具有指导意义。同时为快速获得聚磷酸铵其他体系相图,引入电解质溶液局部组成模型回归了实验体系的溶剂(盐)-盐相互作用能量参数,通过回归参数计算所得的相图与实验相图吻合较好,可用于其他聚磷酸铵体系相图的预测。

磷石膏颗粒湍动流化特性实验及模拟

针对磷石膏颗粒湍动流化体系曳力变化的问题,在实验的基础上,考虑非均匀结构对曳力的影响,引入修正因子φ修正Gidaspow曳力模型,对2D流化床进行了数值模拟研究。通过将Gidaspow模型在不同φ值下的模拟结果与实验结果进行对比,研究φ值的改变对模拟结果的影响规律及一定气速范围内磷石膏颗粒湍动流化体系曳力变化特性。结果表明,Gidaspow模型高估了实验体系曳力,对体系流化特性的预测效果较差;适当φ值的引入能明显提高Gidaspow模型对床层膨胀、压降及体系非均匀度的模拟精度。模拟结果反映出φ值越小,床层膨胀高度越低,床内颗粒浓度分布越不均匀,床层压降波动性越大。随着气速的升高(0.144~0.240 m/s),颗粒沿水平方向上的聚集程度加剧,φ值呈非线性减小(0.31~0.24)。流化体系的非均匀度随着气速增加而增大,颗粒浓度沿径向存在较大梯度,两侧边壁处附近出现环-核结构且流场分布对称性较差。