Applicability of equilibrium and kinetic models on the herbicide 4-chloro-2-methyl phenoxyacetic acid adsorption on bituminous shale

Adsorption characteristics of herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) have been evaluated using bituminous shale (BS) as a model adsorbent-containing solid organic matter in a mineral matrix. The adsorption of MCPA on BS has been studied with varying concentration, temperature, pH and contact time, using batch technique. Adsorption ability of BS increases with increasing temperature and decreasing pH in the studied concentration range of (0.6–4.0) × 10⁻⁴ M. Theoretical curves calculated from Freundlich, Dubinin-Radushkevich (D-R), Langmuir and Temkin isotherm equations show a two-step isotherm shape. The results could be explained by assuming the presence of two-type sites with different affinity on adsorbent surface. Adsorption process is endothermic and entropy controlled at the first stage, and exothermic and enthalpy controlled at the second stage. The mechanism proposed based on surface ionization and complexation model is consistent with the pH dependent experimental results. Kinetic data fit well to both Paterson’s and Nernst Planck model based on homogeneous solid phase diffusion (HSPD). The values of particle diffusion coefficients (D _p ) predicted from both models are comparable each other and independent of temperature and concentration.      

Adsorption Behavior and Inhibition Corrosion Effect of Sodium Carboxymethyl Cellulose on Mild Steel in Acidic Medium

The effect of sodium carboxymethyl cellulose (Na-CMC) on the corrosion behavior of mild steel in 1.0 mol·L⁻¹ HCl solution has been investigated by using weight loss (WL) measurement, potentiodynamic polarization, linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) methods. These results showed that the inhibition efficiency of Na-CMC increased with increasing the inhibitor concentration. Potentiodynamic polarization studies revealed that the Na-CMC was a mixed type inhibitor in 1.0 mol·L⁻¹ HCl. The adsorption of the inhibitor on mild steel surface has been found to obey the Langmuir isotherm. The effect of temperature on the corrosion behavior of mild steel in 1.0 mol·L⁻¹ HCl with addition of 0.04% of Na-CMC has been studied in the temperature range of 298–328 K. The associated apparent activation energy (E^*_a) of corrosion reaction has been determined. Scanning electron microscopy (SEM) has been applied to investigate the surface morphology of mild steel in the absence and presence of the inhibitor molecules.     

Bifunctional sensor of nitric oxide and oxygen based on hematite nanotubes embedded in chitosan matrix

A novel hybrid bifunctional sensing platform for simultaneous determination of NO and O₂ has been developed, whereby hematite nanotubes are immobilized into the chitosan matrix onto a gold electrode (labeled as HeNTs-Chi/Au). The HeNTs distributed in porous-structured chitosan matrix not only offer abundant active sites for bifunctional sensing of NO and O₂, but also facilitate oxidation of NO and reduction of O₂ dramatically. Straight calibration curves are achieved in analyte concentration ranges of 5.0 × 10⁻⁸ to 1.25 × 10⁻⁶ mol L⁻¹ for NO and 2.5 × 10⁻⁷ to 6.0 × 10⁻⁶ mol L⁻¹ for O₂. Also, the detection limits are low of 8.0 × 10⁻⁹ mol L⁻¹ for NO and 5.0 × 10⁻⁸ mol L⁻¹ for O₂. Such an efficient bifunctional sensor for NO and O₂ offers great potential in quantitation of NO levels in biological and medical systems, since NO level is highly regulated by various reactive oxygen species.     

Nickel surface anodic oxidation and electrocatalysis of oxygen evolution

The processes of nickel surface anodic oxidation taking place within the range of potentials preceding oxygen evolution reaction (OER) in the solutions of 1 M KOH, 0.5 M K₂SO₄, and 0.5 M H₂SO₄ have been analyzed in the present paper. Metallic nickel, thermally oxidized nickel, and black nickel coating were used as Ni electrodes. The methods of cyclic voltammetry and X-ray photoelectron spectroscopy were employed. The study was undertaken with a view to find the evidence of peroxide-type nickel surface compounds formation in the course of OER on the Ni electrode surface. On the basis of experimental results and literature data, it has been suggested that in alkaline solution at E ≈ 1.5 V (RHE) reversible electrochemical formation of Ni(IV) peroxide takes place according to the reaction as follows: This reaction accounts for both the underpotential (with respect to ) formation of O₂ from NiOO₂ peroxide and also small experimental values of dE/dlgi slope (<60 mV) at low anodic current densities, which are characteristic for the two-electron transfer process. It has been inferred that the composition of the γ-NiOOH phase, indicated in the Bode and revised Pourbaix diagrams, should be ∼5/6 NiOOH + ∼1/6 NiOO₂. The schemes demonstrating potential-dependent transitions between Ni surface oxygen compounds are presented, and the electrocatalytic mechanisms of OER in alkaline, acid, and neutral medium have been proposed.     

New cut angle quartz crystal microbalance with low frequency-temperature coefficients in an aqueous phase

In a traditional quartz crystal microbalance (QCM), an AT-cut (cut angle φ = 35.25° in yxl orientation) quartz wafer is employed because it has low frequency–temperature coefficients (dF/dT) at room temperature region. But when a QCM is in contact with a liquid phase, its frequency is also related to the properties of the liquid, which are temperature dependent. The value of dF/dT is about 20 Hz/°C for a 9 MHz AT-cut QCM with one side facing water. In this work, a group of QCMs in new cut angles were prepared. The influence of the cut angle on the frequency–temperature characteristic, response sensitivities to surface mass loading and viscodensity of liquid were investigated. An intrinsically temperature-compensated QCM sensor that possesses low dF/dT values in aqueous solution was reported. When a 9 MHz QCM with φ = 35.65° was contacted with water with one side, its dF/dT value is close to zero at ca. 25 °C and its averaged value of |dF/dT| is only 0.6 Hz/°C in the temperature range of 23–27 °C. The frequency responses to surface mass loading and viscodensity of liquid phase are very close among the QCMs with the cut angles in the range of 35.15–35.7°. The intrinsically temperature-compensated QCM was applied to investigate the alternate adsorption processes of cationic polyelectrolyte and silica nanoparticle.     

Influence of polyelectrolyte coating conditions on capillary coating stability and separation efficiency in capillary electrophoresis

Polyelectrolytes are widely used in capillary electrophoresis as coating agents of silica capillaries to prevent adsorption phenomena and improve the repeatability of peptide and protein analysis. A systematic study of the coating experimental conditions has been carried out to optimize coating stability and performance. The main experimental parameters studied were the type and concentration of polyelectrolytes used in several monolayer and multilayer coatings, the ionic strength of coating and stabilizing solutions, and the procedures used for coating and capillary storage. Electroosmotic flow magnitude, direction and repeatability were used to monitor coating stability. Coating ability to limit adsorption was investigated by monitoring variations of migration times, time-corrected peak areas and separation efficiency of test peptides. Capillary-to-capillary and batch-to-batch reproducibility was also studied. In addition, the separation performance of polyelectrolyte coatings were compared to those obtained with bare silica capillaries.     

Neutron powder diffraction as a characterization tool of solid oxide fuel cell materials

Neutron diffraction is a powerful tool for the characterization of materials and, particularly, oxides. Oxide materials find applications in solid oxide fuel cells (SOFCs) as solid electrolytes as well as anode and cathode materials. As a structural probe, neutrons are specially suitable for the crystallographic study of oxides, given the comparable scattering factors of O and other heavier elements, allowing its precise localization in the crystal structure. Many problems can be addressed by neutrons, related to the octahedral tilting in perovskites, phase transitions, order–disorder phenomena, presence of anionic vacancies, etc. Neutrons make possible an accurate determination of the thermal factors and provide a visualization of the diffusion paths in ionic conductors. Neutrons allow the localization of light atoms such as hydrogen, and make possible the distinction between neighbouring elements, typically Fe and Mn. In this work we will describe some recent applications of this technique in the field of solid electrolytes and electrode materials, including some examples from our group.     

Effect of metal ion loaded in a resin towards fluoride retention

Indion FR 10 is a commercially available ion exchange resin with sulphonic acid functionality named as H⁺ form, has appreciable defluoridation capacity (DC). It has been chemically modified to La³⁺, Fe³⁺, Ce³⁺ and Zr⁴⁺ forms by incorporating respective metal ions into the resin in order to know their fluoride selectivity by measuring the DC of the respective resin. The maximum DC of these chemically modified ion exchange resins namely La³⁺, Fe³⁺, Ce³⁺ and Zr⁴⁺ forms were found to be 469.7, 467.5, 456.3 and 470.9 mg F⁻/kg respectively suggests their higher selectivity towards fluoride than H⁺ form which has the DC of only 275 mg F⁻/kg at 11 mg/L initial fluoride concentration. The higher DC of the modified resins was explained by electrostatic adsorption and complexation whereas H⁺ form retains fluoride by hydrogen bond. The functional groups present in the sorbents were identified by FTIR and the existence of fluoride onto the resins was confirmed by EDAX analysis. The experimental data was fitted with both Freundlich and Langmuir isotherms. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° indicate that the nature of sorption is spontaneous and endothermic. The applicability of reaction-based and diffusion-based kinetic models was investigated. A field trial was carried out with fluoride water collected from a nearby fluoride-endemic village to test the suitability of these sorbents at field conditions.     

Anchored thiol smectite clay—kinetic and thermodynamic studies of divalent copper and cobalt adsorption

A natural smectite clay sample from Serra de Maicuru, Pará State, Brazil, had aluminum and zirconium polyoxycations inserted within the interlayer space. The precursor and pillarized smectites were organofunctionalized with the silyating agent 3-mercaptopropyltrimethoxysilane. The basal spacing of 1.47 nm for natural clay increased to 2.58 and 2.63 nm, for pillared aluminum, S_Al/SH, and zirconium, S_Zr/SH, and increases in the surface area from 44 to 583 and 585 m² g⁻¹, respectively. These chemically immobilized clay samples adsorb divalent copper and cobalt cations from aqueous solutions of pH 5.0 at 298±1 K. The Langmuir, Redlich-Peterson and Toth adsorption isotherm models have been applied to fit the experimental data with a nonlinear approach. From the cation/basic center interactions for each smectite at the solid-liquid interface, by using van’t Hoff methodology, the equilibrium constant and exothermic thermal effects were calculated. By considering the net interactive number of moles for each cation and the equilibrium constant, the enthalpy, Δ_intH⁰ (−9.2±0.2 to −10.2±0.2 kJ mol⁻¹) and negative Gibbs free energy, Δ_intG⁰ (−23.9±0.1 to −28.7±0.1 kJ mol⁻¹) were calculated. These values enabled the positive entropy, Δ_intS⁰ (51.3±0.3 to 55.0±0.3 JK⁻¹ mol⁻¹) determination. The cation-sulfur interactive process is spontaneous in nature, reflecting the favorable enthalpic and entropic results. The kinetics of adsorption demonstrated that the fit is in agreement with a second-order model reaction with rate constant k₂, varying from 4.8×10⁻² to 15.0×10⁻² and 3.9×10⁻² to 12.2×10⁻² mmol⁻¹ min⁻¹ for copper and cobalt, respectively.