Extraction of rare-earth elements with solutions of di-(2-ethylhexyl)phosphoric acid in flow-through system under local vibrational treatment

Results obtained in a study of the influence exerted by the vibrational treatment in the dynamic interfacial layer on the extraction of rare-earth elements with solutions of di-(2-ethylhexyl)phosphoric acid in a diluent in a flow-through system are presented. It was shown that the coefficient of extraction acceleration under a local vibrational treatment of the dynamic interfacial layer is smaller than that in the static system and is determined by the nature of an element being extracted and a solvent, frequency and amplitude of oscillations of the vibration element, and fluid flow rate. The degree of extraction of rare-earth elements in a certain time is noticeably higher and can reach a double excess if there is a local vibrational treatment of the dynamic interfacial layer. In this case, the accumulation of a lanthanide in the dynamic interfacial layer is substantially lower, and it does not exceed 10% of the total amount of rare-earth elements in the system.     

Extraction of Rare-Earth Elements with Solutions of <Emphasis Type="Italic">tri</Emphasis>-<Emphasis Type="Italic">n</Emphasis>-Butyl Phosphate under Local Vibrational Impact in Static and Flow-through Systems

Results are presented of a study of the influence exerted by a local vibrational impact in the dynamic interfacial layer on the extraction of rare-earth elements with tri-n-butyl phosphate solutions in a diluent in static and flow-through systems. It is shown that, in the case of local vibrations in the dynamic interfacial layer, the extraction acceleration factor is determined by the nature of a diluent, vibration frequency of the vibrating element, and fluid motion rate and is nearly independent of the nature of an element being extracted.     

Adsorption of phenyl phosphate on Ni-Cr alloy surface: Experimental and theoretical investigations

The adsorption behaviour of phenyl phosphate, which is an available biomolecule, on NiCr alloys was investigated. Atomic flame spectroscopy was used to characterize the elemental dissolution during immersion in neutral aqueous solution of 0.09 w% sodium chloride, 37°C. Phenyl phosphate is shown to reduce the release of both Ni²⁺ and Cr³⁺ ions. XPS analyses evidence the formation of a passive film which is mainly consisted in dichromium trioxide and an ultrafilm layer of phenyl phosphate is adsorbed at the passive film surface. DFT+U calculations show that the phenyl phosphate self-assembling at a Cr₂O₃ surface is thermodynamically favoured, with calculated adsorption energy of 2.9 eV. The first half of this value is due to the interaction with the surface, and the second one is due to self-assembling. This study suggests that phenyl phosphate has an important capacity to prevent, in neutral liquid environment, the release of Cr-Ni surface ions thanks to self-assembling in an inner sphere adsorption on the passive film surface. The phosphate group is covalently anchored to the surface. However, the phenyl ring has two roles: (i) it strongly contributes to the self-assembling and (ii) it acts as a hydrophobic function.     

Graphdiyne: Bridging SnO2 and Perovskite in Planar Solar Cells

The matching of charge transport layer and photoactive layer is critical in solar energy conversion devices, especially for planar perovskite solar cells based on the SnO₂ electron‐transfer layer (ETL) owing to its unmatched photogenerated electron and hole extraction rates. Graphdiyne (GDY) with multi‐roles has been incorporated to maximize the matching between SnO₂ and perovskite regarding electron extraction rate optimization and interface engineering towards both perovskite crystallization process and subsequent photovoltaic service duration. The GDY doped SnO₂ layer has fourfold improved electron mobility due to freshly formed C?O σ bond and more facilitated band alignment. The enhanced hydrophobicity inhibits heterogeneous perovskite nucleation, contributing to a high‐quality film with diminished grain boundaries and lower defect density. Also, the interfacial passivation of Pb?I anti‐site defects has been demonstrated via GDY introduction.     

Purity Considerations and Interfacial Behavior of Solvent Extraction Systems

Abstract

The techniques to purify different components of a typical solvent extraction system, viz., n-hexane/di(2-ethylhexyl)phosphoric acid (HDEHP)/CaCl₂ solution, are described. Data showing how the purity of the different components affects the interfacial tension (γ) are given. The interfacial behavior of the n-hexane/ HDEHP/0.01 mol dm^?3 CaCl₂ solution system was studied as a function of HDEHP concentration and aqueous phase pH. γ-log [HDEHP] curves were also determined at pH 4 when the aqueous phase contained 0.05 mol dm^?3 MgCl₂, CaCl₂, SrCl₂ or BaCl₂. γ-log [HDEHP] curves revealed interaction of the metal ions with the extractant and exhibited a behavior reminiscent of aggregate formation when the aqueous phase contained Ca²⁺.     

Effect of the self-assembly of collagen on crystallisation of calcium carbonate in aqueous solution

In order to investigate how the self-assembly of organic matrix influences crystallisation and growth of inorganic minerals, we selected collagen as the matrix and conducted three experiments of crystallisation of CaCO₃ in different reaction systems: H₂O system, as-assembled collagen fibrils system and self-assembling of collagen system. It is found that (i) the self-assembly process of organic matrix had a remarkable effect on the morphology of inorganic minerals: CaCO₃ crystals formed in the as-assembled collagen fibrils system were global clusters and those formed in the self-assembling of collagen system appeared as interlaced networks and (ii) the organic matrix decided the polymorph of crystals: CaCO₃ crystals were calcite in the H₂O system and appeared vaterite in the collagen system. From this study, we can conclude that the self-assembly of collagen fibrils greatly affect the crystallisation and growth of CaCO₃. Such results are significant in understanding the mechanism of biomineralisation in calcified tissues in general, and useful in the synthesis of biominerals.

(a)?CaCO₃ formed in the as-assembled collagen fibrils system. (b)?CaCO₃ formed in the self-assembling of collagen monomer system.The TEM images of samples obtained in the as-assembled collagen fibrils and self-assembling of collagen monomer system, were observed, respectively. The result shows that crystals CaCO₃ formed in the as-assembled collagen fibrils system were global clusters; crystals CaCO₃ formed in the self-assembling of collagen monomer system appeared interlaced networks.     

Studying Interfacial Reactions of Cholesterol Sulfate in an Unsaturated Phosphatidylglycerol Layer with Ozone Using Field Induced Droplet Ionization Mass Spectrometry

Field-induced droplet ionization (FIDI) is a recently developed ionization technique that can transfer ions from the surface of microliter droplets to the gas phase intact. The air-liquid interfacial reactions of cholesterol sulfate (CholSO₄) in a 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) surfactant layer with ozone (O₃) are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Time-resolved studies of interfacial ozonolysis of CholSO₄ reveal that water plays an important role in forming oxygenated products. An epoxide derivative is observed as a major product of CholSO₄ oxidation in the FIDI-MS spectrum after exposure of the droplet to O₃ for 5 s. The abundance of the epoxide product then decreases with continued O₃ exposure as the finite number of water molecules at the air-liquid interface becomes exhausted. Competitive oxidation of CholSO₄ and POPG is observed when they are present together in a lipid surfactant layer at the air-liquid interface. Competitive reactions of CholSO₄ and POPG with O₃ suggest that CholSO₄ is present with POPG as a well-mixed interfacial layer. Compared with CholSO₄ and POPG alone, the overall ozonolysis rates of both CholSO₄ and POPG are reduced in a mixed layer, suggesting the double bonds of both molecules are shielded by additional hydrocarbons from one another. Molecular dynamics simulations of a monolayer comprising POPG and CholSO₄ correlate well with experimental observations and provide a detailed picture of the interactions between CholSO₄, lipids, and water molecules in the interfacial region.     

纳米复合材料中界面动态特性的扫描静电显微技术研究

纳米复合材料中的微观界面结构和界面作用对材料的宏观介电性能, 如介电常数、介电损耗、击穿强度等有十分重要的影响. 本文发展了一种基于扫描静电显微探针技术的测量方法, 可以直接表征二氧化钛/环氧树脂纳米复合材料的微观界面结构及相应的动态介电响应行为. 实验中利用扫描探针的纳米尺度分辨能力, 探测到不同温度下环氧树脂纳米复合材料的局域动态介电响应变化过程, 从而获得纳米颗粒与高分子界面相互作用及极化相关的温度特性. 进一步通过对二氧化钛纳米颗粒进行表面修饰, 得到了两种不同特性的二氧化钛/环氧树脂界面, 验证了不同界面作用引起的复合材料界面区域与非界面区域高分子链介电损耗图像的反差.     

Correlation between Interfacial Structures and Device Performance: The Double-Edged Sword Effect of Lead Iodide in Perovskite Solar Cells

The interfacial electronic structure of perovskite layers and transport layers is critical for the performance and stability of perovskite solar cells (PSCs). The device performance of PSCs can generally be improved by adding a slight excess of lead iodide (PbI₂) to the precursor solution. However, its underlying working mechanism is controversial. Here, we performed a comprehensive study of the electronic structures at the interface between CH₃NH₃PbI₃ and C₆₀ with and without the modification of PbI₂ using in situ photoemission spectroscopy measurements. The correlation between the interfacial structures and the device performance was explored based on performance and stability tests. We found that there is an interfacial dipole reversal, and the downward band bending is larger at the CH₃NH₃PbI₃/C₆₀ interface with the modification of PbI₂ as compared to that without PbI₂. Therefore, PSCs with PbI₂ modification exhibit faster charge carrier transport and slower carrier recombination. Nevertheless, the modification of PbI₂ undermines the device stability due to aggravated iodide migration. Our findings provide a fundamental understanding of the CH₃NH₃PbI₃/C₆₀ interfacial structure from the perspective of the atomic layer and insight into the double-edged sword effect of PbI₂ as an additive.     

Interfacial structure and properties in polystyrene/epoxy bilayer films

The interfacial structure and properties of immiscible deuterated polystyrene (dPS)/epoxy bilayer films were investigated with neutron reflectivity as functions of the composition of the epoxy layer, the thickness of the dPS layer, and the annealing time. We have found that the interfacial width and its growth rate depend strongly on the compositions of the epoxy layer but only weakly on the thickness of the dPS layer. The effect of the resin/crosslinker composition on the interfacial width and its growth rate is likely due to the different near‐surface structures that result for different epoxy stoichiometries. For an ultra‐thin dPS film (thickness = 2R_g), the data suggest a slight suppression of the growth of the interfacial width that could be due to confinement effects for the long‐chain molecules such as have been previously reported for a thickness of less than approximately 4R_g, where R_g is the radius of gyration of polymer molecules. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2653–2660, 2002     

Effect of water on the interfacial structures of room-temperature ionic liquids

The interfacial structures of cyano-based room-temperature ionic liquids play a very important role in reducing friction. However, the presence of water impairs their tribological performance. The interfacial structures and friction forces of 1-ethyl-3-methylimidazolium dicyanamide, [EMIM][DCN], and the effect of water on these structures and forces were investigated using atomic force microscopy. In addition, the interaction of water and [EMIM][DCN] was evaluated using Fourier-transform infrared (FT-IR) spectroscopy. Multiple repulsive layers were observed in the [EMIM][DCN] solution. This solution showed low friction force because these repulsive layers worked as protective layers against friction. On the other hand, the specific repulsive layer characteristics of [EMIM][DCN] could not be observed in a [EMIM][DCN] + 2 wt% H₂O solution. FT-IR results indicated that the layer structure of [EMIM][DCN] was disturbed by the addition of H₂O. Therefore, the solution containing water exhibited a high friction force.     

Ab initio DFT investigations on structure of copper(I) bis-diazine complexes

Supramolecular self-assembling processes of nitrogen bidendated heterocycles are fundamental for the understanding of rules which predestine to their spontaneous formation. In our approach ab initio DFT method has been used to resolve six Cu(I) complexes. The collected data show that only four structures converged into a quasi-tetrahedral [L₂Cu][BF₄] geometry. A special feature in case of the [(bpy–bpz)₂Cu][BF₄] hetero-complex, not observed in case of the corresponding Cu(I) homo-complexes, is the increased participation of p orbitals of the Cu⁺ to the HOMO.     

SnO2双层电子传输层对钙钛矿太阳能电池界面电荷传输的影响

为了改善基于SnO₂电子传输层的钙钛矿太阳能电池的界面电荷传输特性和迟滞现象,我们采用低温溶液处理工艺制备了4种不同类型的SnO₂电子传输层用于钙钛矿太阳能电池,包括由SnCl₄·5H₂O溶胶-凝胶层(Cl₄-SnO₂)、SnCl₂·2H₂O溶胶-凝胶层(Cl₂-SnO₂)和SnO₂纳米颗粒层(NP-SnO₂)与SnO₂胶体层(Col-SnO₂)两两相互作用形成的同质结SnO₂双层电子传输层和Col-SnO₂单层电子传输层;并系统研究了不同SnO₂双层电子传输层对器件光电性能和迟滞现象的影响。通过扫描电镜(SEM)、X射线衍射(XRD)、稳态光致发光(PL)、电化学阻抗(EIS)和稳定性测试等表征证实,在Col-SnO...     

Retardation of Trap-Assisted Recombination in Lead Halide Perovskite Solar Cells by a Dimethylbiguanide Anchor Layer

Reaching the full potential of solar cells based on photo-absorbers of organic-inorganic hybrid perovskites requires highly efficient charge extraction at the interface between perovskite and charge transporting layer. This demand is generally challenged by the presence of under-coordinated metal or halogen ions, causing surface charge trapping and resultant recombination losses. These problems can be tackled by introducing a small molecule interfacial anchor layer based on dimethylbiguanide (DMBG). Benefitting from interactions between the nitrogen-containing functional groups in DMBG and unsaturated ions in CH₃NH₃PbI₃ perovskites, the electron extraction of TiO₂ is dramatically improved in association with reduced Schottky–Read–Hall recombination, as revealed by photoluminescence spectroscopy. As a consequence, the power conversion efficiency of CH₃NH₃PbI₃ solar cells is boosted from 17.14 to 19.1 %, showing appreciably reduced hysteresis. The demonstrated molecular strategy based on DMBG enables one to achieve meliorations on key figures of merit in halide perovskite solar cells with improved stability.     

Effect of TiO2 on Altering Direction of Interfacial Charge Transfer in a TiO2‐Ag‐MPY‐FePc System by SERS

Interfacial charge transfer (CT) is of interest owing to its effect on the performance of molecular photovoltaic (PV) devices. The characteristics and structures of interfacial materials, such as TiO₂ nanoparticles (NPs) in some solar cells, are employed to adjust the CT process. In this study, three kinds of interfacial systems, including a solar cell‐like TiO₂‐Ag‐ p‐mercaptopyridine (MPY)‐ iron phthalocyanine (FePc) system, are compared to investigate the interfacial CT process using surface‐enhanced Raman scattering (SERS) spectroscopy. The SERS results show the significance of TiO₂ NPs in the system on altering the direction and path of the interfacial CT, which is closely associated with the CT enhancement contribution to SERS in such an interfacial system. SERS spectroscopy is expected to be a promising technique for the exploration and estimation of the interfacial CT behavior in PV devices, which may further extend the applications of SERS in the field of solar cells.     

Characterizing the ZrC(111)/c-ZrO2(111) Hetero-Ceramic Interface: First Principles DFT and Atomistic Thermodynamic Modeling

The mechanical and physical properties of zirconium carbide (ZrC) are limited to its ability to deteriorate in oxidizing environments. Low refractory oxides are typically formed as layers on ZrC surfaces when exposed to the slightest concentrations of oxygen. However, this carbide has a wide range of applications in nuclear reactor lines and nozzle flaps in the aerospace industry, just to name a few. To develop mechanically strong and oxygen-resistant ZrC materials, the need for studying and characterizing the oxidized layers, with emphasis on the interfacial structure between ZrC and the oxidized phases, cannot be understated. In this paper, the ZrC(111)//c-ZrO₂ (111) interface was studied by both finite temperature molecular dynamic simulation and DFT. The interfacial mechanical properties were characterized by the work of adhesion which revealed a Zr|OO|Zr|OO//ZrC(111) interface model as the most stable with an oxygen layer from ZrO₂ being deposited on the ZrC(111) surface. Further structural analysis at the interface showed a crack in the first ZrO₂ layer at the interfacial region. Investigations of the electronic structure using the density of state calculations and Bader charge analysis revealed the interfacial properties as local effects with no significant impacts in the bulk regions of the interface slab.     

Interfacial Studies of the Formation of Microemulsions of Water in Carbon Dioxide with Fluorinated Surfactants

Measurements of the interfacial tension, γ, for water-CO₂-perfiuoropoly ether (PFPE) ionic surfactant systems are utilized to understand the surfactant affinity for the various phases and adsorption at the interface. A marked decrease in γ with salinity is observed as salt screens electrostatic repulsion and induces microemulsion formation, as confirmed with dynamic light scattering. In several cases, the interfacial tension goes through an unusual maximum with salinity, which is explained in terms of competition between surfactant affinity for the various phases and microemulsion formation. Fundamental studies of interfacial properties provide important insight for designing surfactants and experimental conditions to achieve the desired properties of water/CO² microemulsions and emulsions.     

Phase Diagrams and Solubilization of Chlorocarbons in Chlorocarbon/Water/Anionic Surfactant/Alcohol Microemulsion Systems

The solubilization abilities of various chlorocarbons were investigated in a middle phase microemulsion system anionic surfactant sodium dodecyl sulfate (SDS) or sodium dodecyl sulfonate (AS)/n-butanol/chlorocarbon/brine with a ε-β fishlike phase diagram. The composition of the balanced interfacial layer of the microemulsion and some other parameters are calculated. The result shows that surfactant little dissolves in water and chlorocarbon phases, while alcohol mainly dissolves in water and oil phases besides in the interfacial layer. The order of the solubilization ability is dichloromethane (CH₂Cl₂) ～ carbon tetrachloride (CCl₄) > tetrachloroethylene (PCE) > o-dichloro-benzene. The solubility of the alcohol decreases with the increase in NaCl concentrations, which should be compensated by the increase in the amount of alcohol as cosolvent (Cs), so as to maintain the balanced interfacial layer. Salinity has little effect on the partition of surfactant between phases.     

Compact layer influence on hysteresis effect in organic–inorganic hybrid perovskite solar cells

Organic–inorganic hybrid perovskite solar cells have attracted great attention due to their high power conversion efficiency and low cost. However, an anomalous hysteresis effect exists in the perovskite solar cells, especially with TiO₂ as the n-type electron extraction layer. In this communication, we prepare two kinds of TiO₂ compact layers using Atomic Layer Deposition (ALD) and Spin-Coating (SC) methods and compare their influences on the hysteresis effect. By efficiency comparison and AC impedance spectroscopy study, we find that the thickness and morphology of compact layer have a significant influence on the hysteresis effect. Compared to the SC approach, the ALD prepared compact layer is ultra-thin with uniform morphology and shows small interfacial capacitance and large recombination resistance, meaning reduced interfacial charge accumulation and accelerated electron transport, which would relieve the hysteresis effect.