Removal of Cd(II), Cu(II), and Pb(II) by adsorption onto natural clay: a kinetic and thermodynamic study

In this work, we study the elimination of three bivalent metal ions (Cd²⁺, Cu²⁺, and Pb²⁺) by adsorption onto natural illitic clay (AM) collected from Marrakech region in Morocco. The characterization of the adsorbent was carried out by X-ray fluorescence, Fourier transform infrared spectroscopy and X-ray diffraction. The influence of physicochemical parameters on the clay adsorption capacity for ions Cd²⁺, Cu²⁺, and Pb²⁺, namely the adsorbent dose, the contact time, the initial pH imposed on the aqueous solution, the initial concentration of the metal solution and the temperature, was studied. The adsorption process is evaluated by different kinetic models such as the pseudo-first-order, pseudo-second-order, and Elovich. The adsorption mechanism was determined by the use of adsorption isotherms such as Langmuir, Freundlich, and Temkin models. Experiments have shown that heavy metals adsorption kinetics onto clay follows the same order, the pseudo-second order. The isotherms of adsorption of metal cations by AM clay are satisfactorily described by the Langmuir model and the maximum adsorption capacities obtained from the natural clay, using the Langmuir isotherm model equation, are 5.25, 13.41, and 15.90 mg/g, respectively for Cd(II), Cu(II), and Pb(II) ions. Adsorption of heavy metals on clay is a spontaneous and endothermic process characterized by a disorder of the medium. The values of ΔH are greater than 40 kJ/mol, which means that the interactions between clay and heavy metals are chemical in nature.     

Fabrication of ZnSe/C Hollow Polyhedrons for Lithium Storage

ZnSe has got extensive attention for high-performance LIBs anode due to its remarkable theoretical capacity and environmental friendliness. Nevertheless, the large volume variation for the ZnSe in the discharge/charge processes brings about rapid capacity fading and poor rate performance. Herein, ZnSe/C hollow polyhedrons are successfully synthesized by selenization of zeolitic imidazolate framework-8 (ZIF-8) with resorcinol-formaldehyde (RF) coating. The protection of C layer derived from RF coating layer and Ostwald ripening during the process of selenization play important roles in promoting formation of ZnSe/C hollow polyhedrons. The ZnSe/C hollow polyhedrons exhibit good rate performance and long-term cycle stability (345 mAh g⁻¹ up to 1000 cycles at 1 A g⁻¹) for lithium ion batteries (LIBs) anode. The improved electrochemical performance is benefit from the unique ZnSe/C hollow structure, in which the hollow structure can effectively avoid terrible volume expansion, and the thin ZnSe/C shell can not only provide adequate diffusion paths of lithium ions and but also enhance the electronic conductivity.     

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.     

Role of FTFSI Anion Asymmetry on Physical Properties of AFTFSI (A=Li,Na and K) Based Electrolytes and Consequences on Supercapacitor Application

This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li⁺, Na⁺ or K⁺) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte.     

Mathematical model of electromigration allowing the deviation from electroneutrality

The structure of the double layer on the boundary between solid and liquid phases is described by various models, of which the Stern–Gouy–Chapman model is still commonly accepted. Generally, the solid phase is charged, which also causes the distribution of the electric charge in the adjacent diffuse layer in the liquid phase. We propose a new mathematical model of electromigration considering the high deviation from electroneutrality in the diffuse layer of the double layer when the liquid phase is composed of solution of weak multivalent electrolytes of any valence and of any complexity. The mathematical model joins together the Poisson equation, the continuity equation for electric charge, the mass continuity equations, and the modified G-function. The model is able to calculate the volume charge density, electric potential, and concentration profiles of all ionic forms of all electrolytes in the diffuse part of the double layer, which consequently enables to calculate conductivity, pH, and deviation from electroneutrality. The model can easily be implemented into the numerical simulation software such as Comsol. Its outcome is demonstrated by the numerical simulation of the double layer composed of a charged silica surface and an adjacent liquid solution composed of weak multivalent electrolytes. The validity of the model is not limited only to the diffuse part of the double layer but is valid for electromigration of electrolytes in general.     

Protein dielectrophoresis: Key dielectric parameters and evolving theory

Globular proteins exhibit dielectrophoresis (DEP) responses in experiments where the applied field gradient factor ∇E² appears far too small, according to standard DEP theory, to overcome dispersive forces associated with the thermal energy kT of disorder. To address this a DEP force equation is proposed that replaces a previous empirical relationship between the macroscopic and microscopic forms of the Clausius–Mossotti factor. This equation relates the DEP response of a protein directly to the dielectric increment δε⁺ and decrement δε⁻ that characterize its β-dispersion at radio frequencies, and also indirectly to its intrinsic dipole moment by way of providing a measure of the protein's effective volume. A parameter Γ_pw, taken as a measure of cross-correlated dipole interactions between the protein and its water molecules of hydration, is included in this equation. For 9 of the 12 proteins, for which an evaluation can presently be made, Γ_pw has a value of ≈4600 ± 120. These conclusions follow an analysis of the failure of macroscopic dielectric mixture (effective medium) theories to predict the dielectric properties of solvated proteins. The implication of a polarizability greatly exceeding the intrinsic value for a protein might reflect the formation of relaxor ferroelectric nanodomains in its hydration shell.     

In situ preparation of hetero-polymers/clay nanocomposites by CUAAC click chemistry

A series of polymer/clay nanocomposites containing mechanistically two different polymers, poly(ethylene glycol) (PEG) and poly(epsilon caprolactone) (PCL), were prepared by simultaneous copper(I)-catalyzed alkyne-azide cycloaddition click reactions. Both clickable polymers, PEG-Alkyne and PCL-Alkyne, were simultaneously clicked on to azide-functional montmorillonite (MMT-N₃) nanoclay to get corresponding PEG-PCL/MMT nanocomposites. The chemical structures of the resulting nanocomposites were verified by following azide and silicone-oxygen bands using FT-IR and characteristic bands of PEG and PCL segments using ¹H-NMR spectroscopy. The combined XRD and TEM analysis confirmed that all PEG-PCL/MMT nanocomposites had partially exfoliated/intercalated morphologies. In addition, the increase of MMT-N₃ loading not only improved the onset and maximum degradation temperatures of the nanocomposites but also their char yields. Furthermore, the incorporation of MMT-N₃ in the polymer matrix did not significantly influence the crystallization behavior of both PEG and PCL segments.     

Composite Polybenzimidazole Membrane with High Capacity Retention for Vanadium Redox Flow Batteries

Currently, energy storage technologies are becoming essential in the transition of replacing fossil fuels with more renewable electricity production means. Among storage technologies, redox flow batteries (RFBs) can represent a valid option due to their unique characteristic of decoupling energy storage from power output. To push RFBs further into the market, it is essential to include low-cost materials such as new generation membranes with low ohmic resistance, high transport selectivity, and long durability. This work proposes a composite membrane for vanadium RFBs and a method of preparation. The membrane was prepared starting from two polymers, meta-polybenzimidazole (6 μm) and porous polypropylene (30 μm), through a gluing approach by hot-pressing. In a vanadium RFB, the composite membrane exhibited a high energy efficiency (~84%) and discharge capacity (~90%) with a 99% capacity retention over 90 cycles at 120 mA·cm⁻², exceeding commercial Nafion^® NR212 (~82% efficiency, capacity drop from 90% to 40%) and Fumasep^® FAP-450 (~76% efficiency, capacity drop from 80 to 65%).     

钙钛矿太阳能电池电子传输层的制备及应用

目前,有机-无机杂化钙钛矿太阳能电池(PSC)的器件效率已经超过25％.电子传输层作为PSC中的重要组成部分在提取和传输光生电子,阻挡空穴,修饰界面,调节界面能级和减少电荷复合等方面起着关键作用.无机n型材料,例如TiO2、ZnO、SnO2和其他金属氧化物材料具有成本低和稳定性好的特点,经常在传统PSC中被用作电子传输...