A novel solution–solid synthesis method for preparation of ZnO and Au/ZnO composite nanocrystals using starch matrix has been developed and optimized. The process is characterized by simplicity, environmental compatibility and good performance. Nanocomposite samples with different gold content have been synthesized and studied with respect to their structure, size and shape of nanocrystals, thermal behavior, surface characteristics and optical properties, as well as their photocatalytic activity. We have found that modification of nanocrystalline ZnO with gold nanocrystals strongly influences the porosity of nanocomposites - less micro- and mesopores are formed, which results in a reduced specific surface area. The synthesized ZnO and Au/ZnO nanocrystals are active photocatalysts for the photocatalytic degradation of methylene blue (MB), as a model pollutant dye, in the UV region. There is a decrease in photocatalytic activity with an increase of the gold content in the nanocomposite photocatalyst. The degree of MB degradation obtained with a pure ZnO sample is comparable to that with the Au/ZnO photocatalyst with the lowest gold content 0.05 at. %. New and interesting result has been obtained relating to maximum specific (intrinsic) photocatalytic activity of 0.05 at. % Au/ZnO nanocrystals.
The methods to study capillary waves have been reviewed together with the emerging practical applications of theirs and new theoretical developments in the field. The focus is on monochromatic ripples of frequency in the range 0.1–10 kHz. A capillary wave apparatus has been constructed that combines several recent advances on the technique. It is based on the profilometry of waves decaying with distance, with a high-speed video camera detecting the light refracted by the surface. A code to process the images has been developed, which executes a regression analysis to determine the characteristics of the wave. High precision and accuracy have been achieved: standard deviation from the mean of ±0.5% for the wavelength and ±7% for the decay length; mean deviations from the theoretical values ±0.2% for the wavelength and ±5% for the decay length. An analytic approximation for the dispersion relation has been used to determine the Gibbs elasticity of a surfactant monolayer from the data for decay length vs frequency. The elasticity of an octanol monolayer has been determined with precision of ±1 mN/m, in excellent agreement with the theoretical value. Surface tension can be measured from the wavelength data with precision of ±0.3 mN/m. It has been demonstrated that the effect of the surface elasticity on the wavelength is significant, and accurate wavelength data can actually be used to determine the elasticity if the surface tension is known.
The article summarizes the results of our research on the behavior of ions at uncharged fluid interfaces, with a focus on moderately to highly concentrated aqueous electrolytes. The ion-specific properties of such interfaces have been analyzed. The ion-specificity series are different for water|air and water|oil; different for surface tension σ, surface Δχ potential and electrolyte adsorption, and they change with concentration. A methodology has been developed that allows to disentangle the multiple factors controlling the ion order. The direct ion-surface interactions are not always the most significant factor behind the observed ion sequences: indirect effects stemming from conjugate bulk properties are often more important. For example, the order of the surface tension with the nature of the anion (σKOH > σKCl > σKNO3 for potassium salts) is often the result of bulk nonideality and follows the order of the bulk activity coefficients (γKOH > γKCl > γKNO3) rather than that of a specific ion-surface interaction potential. The surface Δχ potential of aqueous solutions is, in many cases, insensitive to the ion distribution in the electric double layer but reflects the orientation of water at the surface, through the ion-specific dielectric permittivity ε of the solution. Even the sign of Δχ is often the result of the decrement of ε in the presence of electrolyte. A whole new level of complexity appears when the ions interact with an uncharged surfactant monolayer. A method has been developed to measure the electrolyte adsorption isotherms on monolayers of varying area per surfactant molecule via a combination of experiments-compression isotherms and surface pressure of equilibrium spread monolayers. The obtained isotherms demonstrate that the ions exhibit a maximum in their adsorption on monolayers of intermediate density. The maximum is explained with the interplay between ion-surfactant complexation, volume exclusion and osmotic effects.
17 March 2023 in The Journal of Physical Chemistry B
The interaction of several simple electrolytes with uncharged insoluble monolayers is studied on the basis of tensiometric and potentiometric data for the surface electrolyte solution|air. The induced adsorption of electrolyte on the monolayer is determined via a combination of data for equilibrium spreading pressure and surface pressure versus area isotherms. We show that the monolayer-induced adsorption of electrolyte is not only strongly ion-specific but also surfactant-specific. The comparison between the ion-specific effects on a carboxylic acid monolayer at low pH and an ester monolayer shows that the anion series follows the same order while the cation series reverses. The effect of the electrolyte on the chemical potential of the monolayer shows attraction between the surfactant and the ions at low monolayer densities, but at high surface densities, repulsion seems to come into play. In nearly all investigated cases, a maximum of monolayer-induced electrolyte adsorption is observed at intermediate monolayer densities. This suggests specific interactions between the surfactant headgroup and the ions. The Volta potential data for the monolayers are analyzed on the basis of the equations of quadrupolar electrostatics. The analysis suggests that the ion-specific effect on the Volta potential is due to the ion-specific decrement of the bulk dielectric constant of the electrolyte solution. Moreover, we present evidence that in most cases the effect of the electrolyte on the orientation of the adsorbed dipoles cannot be neglected. Instead, the change in the ion distribution in the electric double layer seems to have a small effect on the Volta potential.
Modeling of adsorption-based removal technologies for fluorosurfactants requires accurate simulation methods which can predict their adsorption isotherm and monolayer structure.
11 May 2023 in The Journal of Physical Chemistry Letters
The interactions between ions and lipid monolayers have captivated the attention of biologists and chemists alike for almost a century. In the absence of experimentally accessible concentration profiles, the electrolyte adsorption remains the most informative quantitative characteristic of the ion-lipid interactions. However, there is no established procedure to obtain the electrolyte adsorption on spread lipid monolayers. As a result, in the literature, the ion-lipid monolayer interactions are discussed qualitatively, based on the electrolyte effect on more easily accessible variables, e.g., surface tension. In this letter, we demonstrate how the electrolyte adsorption on lipid monolayers can be obtained experimentally. The procedure requires combining surface pressure versus molecular area compression isotherms with spreading pressure data. For the first time, we report an adsorption isotherm of NaCl on a lipid monolayer as a function of the density of the monolayer. The leading interactions seem to be the osmotic effect from the lipid head groups in the surface layer and ion-lipid association.