离子型稀土矿山淋洗及尾水富集试验研究

对浸矿后离子型稀土原地浸矿场采用清水进行淋洗，在184天的清水淋洗过程中，尾水氨氮值从最开始的507mg/L，降低至140mg/L，淋洗尾水pH4.52~3.10。淋洗尾水采用两级反渗透膜分离，既回收有价资源稀土，又能使出水氨氮达标。结果表明，产水氨氮浓度稳定低于15mg/L，对稀土的截留率高于98.25%，浓水中稀土离子平均浓度313.4mg/L，可进一步回收稀土资源。     

Direct View on the Origin of High Li+ Transfer Impedance in All-Solid-State Battery

Large interfacial resistance plays a dominant role in the performance of all-solid-state lithium-ion batteries. However, the mechanism of interfacial resistance has been under debate. Here, the Li⁺ transport at the interfacial region is investigated to reveal the origin of the high Li⁺ transfer impedance in a LiCoO₂(LCO)/LiPON/Pt all-solid-state battery. Both an unexpected nanocrystalline layer and a structurally disordered transition layer are discovered to be inherent to the LCO/LiPON interface. Under electrochemical conditions, the nanocrystalline layer with insufficient electrochemical stability leads to the introduction of voids during electrochemical cycles, which is the origin of the high Li⁺ transfer impedance at solid electrolyte-electrode interfaces. In addition, at relatively low temperatures, the oxygen vacancies migration in the transition layer results in the formation of Co₃O₄ nanocrystalline layer with nanovoids, which contributes to the high Li⁺ transfer impedance. This work sheds light on the mechanism for the high interfacial resistance and promotes overcoming the interfacial issues in all-solid-state batteries.     

A Highly Sensitive,Reversible, and Bidirectional Humidity Actuator by Calcium Carbonate Ionic Oligomers Incorporated Poly(Vinylidene Fluoride)

Sensitivity and multi-directional motivation are major two factors for developing optimized humidity-response materials, which are promising for sensing, energy production, etc. Organic functional groups are commonly used as the water sensitive units through hydrogen bond interactions with water molecules in actuators. The multi-coordination ability of inorganic ions implies that the inorganic ionic compounds are potentially superior water sensitive units. However, the particle forms of inorganic ionic compounds produced by classical nucleation limit the number of exposed ions to interact with water. Recent progress on the inorganic ionic oligomers has broken through the limitation of classical nucleation, and realized the molecular-scaled incorporation of inorganic ionic compounds into an organic matrix. Here, the incorporation of hydrophilic calcium carbonate ionic oligomers into hydrophobic poly(vinylidene fluoride) (PVDF) is demonstrated. The ultra-small calcium carbonate oligomers within a PVDF film endow it with an ultra-sensitive, reversible, and bidirectional response. The motivation ability is superior to other bidirectional humidity-actuators at present, which realizes self-motivation on an ice surface, converting the chemical potential energy of the humidity gradient from ice to kinetic energy.     

Probing the effect of R-cation radii on structural,vibrational, optical,and dielectric properties of rare earth (R=La,Pr, Nd) aluminates

The present study correlates the effect of R-cation radii on structural, vibrational, optical, and dielectric properties of rhombohedral rare earth aluminates RAlO₃ (R = La, Pr, Nd). The polycrystalline samples of RAlO₃ have been synthesized using sol-gel synthesis technique. Pure rhombohedral phase of RAlO₃ samples has been confirmed with X-ray diffraction. Systematic decrements in the lattice parameter, bond length, and bond angle have been observed, giving rise to structural distortion due to decrease in ionic radii of R-cation. The phononic properties of RAlO₃ have been investigated through Raman spectroscopy, where the degree of distortion of AlO₆ octahedra can be analyzed with the peak position of E_g and A_1g modes. An increase in the energy bandgap with decreasing R-cation radii shows an interconnection with the decrease in Al–O bond length. Interestingly, the decreasing dielectric constant with decreasing ionic radii of R-cation has been correlated with the difference in electronegativity of cation(R³⁺)-anion(O^2?) pair. Also, a positive linear relationship between dielectric constant and energy bandgap has been investigated using Penn model.     

Investigation on La3+ and Dy3+ co-doped ceria ceramics with an optimized average atomic number of dopants for electrolytes in IT-SOFCs

In the present study, we investigate the fundamental properties of CeO₂ by selecting La³⁺ (57), and Dy³⁺ (66) as dopants with optimized average atomic number of 61.5, which lies in between Pm³⁺ (62) and Sm³⁺ (62) in accordance with the criteria for optimum doping. A system of co-doped ceria ceramics Ce_1–x–yLa_xDy_yO_2-δ ((x, y) = (0.00, 0.00), (0.025, 0.025), (0.05, 0.05), (0.075, 0.075), (0.10, 0.10), (0.00, 0.20) and (0.20, 0.00)) as electrolytes for intermediate temperature solid oxide fuel cells were successfully prepared by a well-known sol-gel auto-combustion route. In order to obtain dense samples, the prepared pellets were sintered in air at 1300 °C for 4 h using conventional furnace and relative densities of all the samples were found to be higher than 95%. Single phase cubic structure, microstructural density and elemental composition analysis of all the samples were studied by powder X-ray diffraction, scanning electron microscope and energy dispersive spectroscopy techniques, respectively. Raman spectroscopy analysis confirmed the formation of concentrated O^2-–vacancies in the co-doped ceria system. Impedance spectroscopy measurements revealed the high value of total ionic conductivity and low activation energy for the composition Ce_0.85La_0.075Dy_0.075O_2?δ i.e., 2.08 × 10^–2 S cm^–1 and 0.58 eV, respectively. Linear thermal expansion analyses of all the samples revealed the matched thermal expansion coefficients. Finally, these results recommend that the Ce_0.85La_0.075Dy_0.075O_2?δ sample can be useful as a solid electrolyte in IT-SOFC applications.     

Magnetic nanocellulose hybrid nanoparticles and ionic liquid for extraction of neonicotinoid insecticides from milk samples prior to determination by liquid chromatography-mass spectrometry

A simple and rapid microextraction procedure is reported on the use of ionic liquid in combination with magnetic nanocellulose hybrid nanoparticles. The procedure is ultrasound-assisted and applicable to selective preconcentration of neonicotinoid insecticides from milk samples, prior to being analysed by liquid chromatography-mass spectrometry. The extraction procedure uses small volume of organic solvents (<1 mL), and there is no need for centrifugation. In the experimental approach the ionic liquid was quickly disrupted by an ultrasonic probe and dispersed in milk samples in a cloudy form. At this stage, neonicotinoid insecticides were extracted into the fine droplets of ionic liquid. Then small amounts of magnetic nanocellulose hybrid nanoparticles were dispersed into the sample solutions to adsorb the ionic liquid containing the analytes and phase separation was completed. The ionic liquid allowed the microextraction of the analytes and a small volume of acetonitrile was used for elution. Magnetic nanocellulose favoured the adsorption of the ionic liquid with the analytes and improved the final recovery with respect to the use of simple magnetic nanoparticles as a sorbent material. Under the optimum conditions, decision capabilities were achieved in the 0.02–0.06 mg kg^?1 range, with recoveries between 91.0% and 109.5%.     

Thermodynamic assessment of the Ga–Se–Te system

In this study, the Ga–Te binary system was reassessed by means of the CALPHAD method using a modified lattice stability parameter for Te as well as experimental data for this binary system. The two-sublattice ionic solution model was applied for the liquid phase, and the intermediate phases were described by the sublattice model. A set of self-consistent thermodynamic parameters was optimized for all the phases in the Ga–Te binary system, which reproduced the phase diagram and the thermodynamic properties well. Using the reevaluated Ga–Te system, previously assessed Ga–Se system, and modified Se–Te system, a critical evaluation of the Ga–Se–Te ternary system was performed. The calculated vertical sections, isothermal sections, and liquidus projection agreed reasonably well with the experimental data. Immiscibility in the liquid phase was observed, and the origin of this behavior is discussed from a thermodynamic perspective.     

Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. The porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.     

Effect of the doping time of the 1‐butyl‐3‐methylimidazolium ionic liquid cation on the Nafion membrane proprieties

Nafion membranes were prepared by incorporating in the polymer matrix the 1‐butyl‐3‐methylimidazolium (BMI⁺) ionic liquid cation at different doping levels. Increasing the doping time of the membranes with the ionic liquid results in increased incorporation of the BMI⁺ cation but a decrease in the bulk conductivity. The thermogravimetric analysis shows that the BMI⁺ cation incorporation increases the thermal stability of the membranes. The higher discharge efficiency of the fuel cell at 80°C was obtained by using Nafion membrane after 15 minutes of doping in the ionic liquid solution.