Photocatalytic degradation of bisphenol A in aqueous solution using TiO2/clinoptilolite hybrid photocatalyst.

Photocatalytic degradation of bisphenol A (BPA) was investigated using commercial TiO2 P25 nanoparticles supported on natural zeolite clinoptilolite (Cli). Employing ultrasound assisted solid-state dispersion method hybrid photocatalyst containing 20 wt% of TiO2, marked TCli-20, was prepared. The structural, morphological and surface properties, and particle size distribution of TCli-20 were studied by X-ray powder diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, scanning electron microscopy with energy dispersive spectroscopy, atomic force microscopy, Brunner-Emmet-Teller method and laser diffraction. The results revealed a successful loading of TiO2 P25 nanoparticles on Cli surface and the preservation of both zeolitic structure and optical properties of TiO2. The influence of catalyst dose, pH value and the addition of hydrogen peroxide (H2O2) was evaluated. The optimal reaction conditions were 2 g/L of catalyst at near-neutral conditions (pH = 6.4) for complete BPA (5 mg/L) photodegradation after 180 min of exposure to simulated solar light. The addition of H2O2 was beneficial for the degradation process and led to the removal of BPA after 120 min of irradiation. BPA removal (60% for 180 min of irradiation) was reduced when TCli-20 was tested in bottled drinking water due to the presence of bicarbonate ions which acted as scavengers for hydroxyl radicals. Even though the photocatalytic activity of TCli-20 decreased after several cycles of usage, 70% of BPA was still successfully degraded during the fourth cycle. The reusability study showed easy separation, stability and good photocatalytic ability of investigated cost-effective hybrid photocatalyst.

Enhancement of ZnO@RuO2 bifunctional photo-electro catalytic activity toward water splitting.

Catalytic materials are the greatest challenge for the commercial application of water electrolysis (WEs) and fuel cells (FCs) as clean energy technologies. There is a need to find an alternative to expensive and unavailable platinum group metal (PGM) catalysts. This study aimed to reduce the cost of PGM materials by replacing Ru with RuO2 and lowering the amount of RuO2 by adding abundant and multifunctional ZnO. A ZnO@RuO2 composite in a 10:1 molar ratio was synthesized by microwave processing of a precipitate as a green, low-cost, and fast method, and then annealed at 300°C and 600°C to improve the catalytic properties. The physicochemical properties of the ZnO@RuO2 composites were investigated by X-ray powder diffraction (XRD), Raman and Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), UV-Vis diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. The electrochemical activity of the samples was investigated by linear sweep voltammetry in acidic and alkaline electrolytes. We observed good bifunctional catalytic activity of the ZnO@RuO2 composites toward HER and OER in both electrolytes. The improved bifunctional catalytic activity of the ZnO@RuO2 composite by annealing was discussed and attributed to the reduced number of bulk oxygen vacancies and the increased number of established heterojunctions.

Goat milk proteins enriched with Agaricus blazei Murrill ss. Heinem extracts: Electrophoretic, FTIR, DLS and microstructure characterization.

This study aimed to characterize mixtures of goat milk proteins and Agaricus blazei Murrill (ABM) extracts (aqueous, AE and polysaccharides, PE). The mixtures showed stable particles with ζ-potential more negative than -41.1 mV. The addition of AMB extracts to goat milk did not result in a significant particle size change, whereas their addition to heated goat milk significantly increased mean particle diameter (from 194 nm to 225 nm). Fourier Transform Infrared Spectroscopy (FTIR) showed that ABM extracts provoked changes in the secondary structure of goat milk proteins and interactions between polysaccharides and milk proteins predominantly via hydrogen and/or glycoside bonds and hydrophobic interactions. The milk protein profiles revealed proteolytic activity in mixtures with AE resulting in the formation of five new polypeptides. The different microstructures of mixtures with AE and PE were found by Scanning Electron Microscopy (SEM). A schematic representation of possible milk proteins-ABM extracts interactions has been given.

Bifunctional catalytic activity of Zn1-xFexO toward the OER/ORR: seeking an optimal stoichiometry.

Eco-friendly and rapid microwave processing of a precipitate was used to produce Fe-doped zinc oxide (Zn1-xFexO, x = 0, 0.05, 0.1, 0.15 and 0.20; ZnO:Fe) nanoparticles, which were tested as catalysts toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in a moderately alkaline solution. The phase composition, crystal structure, morphology, textural properties, surface chemistry, optical properties and band structure were examined to comprehend the influence of Zn2+ partial substitution with Fe3+ on the catalytic activity of ZnO:Fe. Linear sweep voltammetry showed an improved catalytic activity of ZnO:5Fe toward the ORR, compared to pure ZnO, while with increased amounts of the Fe-dopant the activity decreased. The improvement was suggested by a more positive onset potential (0.394 V vs. RHE), current density (0.231 mA cm-2 at 0.150 V vs. RHE), and faster kinetics (Tafel slope, b = 248 mV dec-1), and it may be due to the synergistic effect of (1) a sufficient amount of surface oxygen vacancies, and (2) a certain amount of plate-like particles composed of crystallites with well developed (0001) and (0001[combining macron]) facets. Quite the contrary, the OER study showed that the introduction of Fe3+ ions into the ZnO crystal structure resulted in enhanced catalytic activity of all ZnO:Fe samples, compared to pure ZnO, probably due to the modified binding energy and an optimized band structure. With the maximal current density of 1.066 mA cm-2 at 2.216 V vs. RHE, an onset potential of 1.856 V vs. RHE, and the smallest potential difference between the OER and ORR (ΔE = 1.58 V), ZnO:10Fe may be considered a promising bifunctional catalyst toward the OER/ORR in moderately alkaline solution. This study demonstrates that the electrocatalytic activity of ZnO:Fe strongly depends on the defect chemistry and consequently the band structure. Along with providing fundamental insight into the electrocatalytic activity of ZnO:Fe, the study also indicates an optimal stoichiometry for enhanced bifunctional activity toward the OER/ORR, compared to pure ZnO.

Influence of heat treatment of goat milk on casein micelle size, rheological and textural properties of acid gels and set type yoghurts.

Acid gels and yoghurts were made from goat milk that was heated at 72°C/30 s, 85°C/5 min, and 95°C/5 min, followed by acidification with starter culture at 43C until pH 4.6. The rheological and textural properties of acid gels and yoghurts were analyzed using dynamic low amplitude oscillatory rheology and back extrusion texture analysis, respectively. The effect of goat milk heat treatment on the mean casein micelle diameter and protein profile was also determined by dynamic light scattering and SDS PAGE electrophoresis, respectively. The shortest gelation and fermentation time was recorded for yoghurt prepared from milk heated at 85°C/5 min. Also, the pH of gelation, the storage moduli (G') and yield stress were higher for this yoghurt, compared with the other two. Textural properties of goat milk yoghurts such as firmness and consistency were strongly affected by milk heat treatment, and the highest values were recorded for yoghurt produced from milk preheated at 85°C/5 min, as well. The largest casein micelles were measured after 85°C/5 min treatment and their size decreased at higher temperature, despite higher denaturation of whey proteins at the most intense heat regime, indicating the structure changes that influence on the acid gelation.

Irregular influence of alkali metals on Cu-SAPO-34 catalyst for selective catalytic reduction of NOx with ammonia.

SCR activity of Cu-SAPO-34 catalyst was reduced by alkali metal ions. The alkali metals ions (Li+, Na+ and K+) have shown irregular influences on Cu-SAPO-34. The order of poisoning strengths under 400 °C was found to be: Na+ > K+ > Li+, which is not consistent with the basicities of their corresponding metals. Experimental results and calculations showed that the alkali metal ions readily replace H+ and Cu2+/Cu+ ions. These exchanges result in the loss of Brønsted acid sites and migration of isolated Cu2+ ions in Cu-SAPO-34, which decrease the NH3-SCR activity. Both the basicity and ion diameter will affect the exchanging behavior of an alkali ion. Na+ and Li+ ions will influence both H+ and Cu2+/Cu+ ions but K+ ions only preferably replace the H+. We hypothesize that K+ cannot enter into a small ring (6-membered ring) to replace a Cu2+/Cu+ ion because of its large ion diameter. The displaced Cu2+/Cu+ ions will transfer to adjacent unbonded Al site to form a CuAlO2 species.

Promoting effects of water on the NH3-SCR reaction over Cu-SAPO-34 catalysts: transient and permanent influences on Cu species.

Cu-SAPO-34 catalysts with varied Cu loadings were synthesized through ion exchange to study the influence of water on the NH3-SCR reaction. The catalytic activities were evaluated by selective catalytic reduction of NO under a reactant feed in the presence/absence of water. Transient experiments were designed to study the response of NO conversion to the presence of water. H2-TPR and DFT calculations were performed to study the reducibility of Cu species. NH3-TPD and XPS were conducted to reveal the migration of Cu species. The results show that water could remarkably improve NO reduction activities and the promoting effect is more significant on the catalyst with low Cu loading. Both transient and permanent influences were found in this promoting phenomenon. For the transient influence, water has been proved to accelerate the re-oxidation half-cycle. Moreover, water can enhance the promoting effect of the SCR feed on the migration of Cu species. These unanchored Cu ions migrate to defect sites to form active sites, which lead to a permanent influence of water.

PVA Cryogel as model hydrogel for iontophoretic transdermal drug delivery investigations. Comparison with PAA/PVA and PAA/PVP interpenetrating networks.

The use of polyvinyl alcohol (PVA) cryogel as a model hydrogel for iontophoretic transdermal investigations is proposed. Due to the excellent combination of its properties, it could be used for evaluating iontophoretic transdermal delivery of variety of drugs, regardless of pKa, pH or presence of auxiliary ions. Applicability of PVA Cryogel for drug delivery purposes was compared to those of polyacrylic acid/polyvinyl alcohol (PAA/PVA) and polyacrylic acid/polyvinylpyrrolidone (PAA/PVP) adhesive interpenetrating networks. Swelling properties of PVA Cryogel were shown to be almost independent on pH and NaCl concentration, while swelling of PAA-based gels was significantly affected. Addition of PVA and PVP to PAA decreased swelling degrees and increased adhesivity and compression moduli. Iontophoretic experiments were performed using a donor gel/skin/receptor gel configuration; current density and delivery duration were varied. Dexamethasone sodium phosphate was used as model drug molecule. PVA Cryogel was used for investigating the influence of NaCl concentration, which can alter the amount of current carried by the drug ions and, therefore, the delivery rate. By using PVA Cryogel it was possible to easily determine the amount of drug permeated through the skin into the receptor gel, the amount retained by the skin and the amount remained in the donor hydrogel. Decreasing NaCl concentration in PVA Cryogel resulted in higher total amounts of drug delivered and significantly enhanced drug permeation through the lower layers of the skin into the receptor hydrogel.

Surfactant-assisted microwave processing of ZnO particles: a simple way for designing the surface-to-bulk defect ratio and improving photo(electro)catalytic properties.

ZnO nanopowders were produced using microwave processing of a precipitate and applied as a photoanode for photoelectrochemical water splitting. Two different surfactants, cetyltrimethylammonium bromide (CTAB) as the cationic and Pluronic F127 as the non-ionic one, were employed to in situ adjust the surface-to-bulk defect ratio in the ZnO crystal structure and further to modify the photo(electro)catalytic activity of the ZnO photoanode. The crystal structure, morphological, textural, optical and photo(electro)catalytic properties of ZnO particles were studied in detail to explain the profound effects of the surfactants on the photoanode activity. The ZnO/CTAB photoanode displayed the highest photocurrent density of 27 mA g-1, compared to ZnO (10.4 mA g-1) and ZnO/F127 photoanodes (20 mA g-1) at 1.5 V vs. SCE in 0.1 M Na2SO4 under visible illumination of 90 mW cm-2. A significant shift of the overpotential toward lower values was also observed when photoanodes were illuminated. The highest shift of the overpotential, from 1.296 to 0.248 V vs. SCE, was recorded when the ZnO/CTAB photanode was illuminated. The ZnO/CTAB photoanode provides efficient charge transfer across the electrode/electrolyte interface, with a longer lifetime of photogenerated electron-hole pairs and reduced possibility of charge recombination. The photoconversion efficiency was improved from 1.4% for ZnO and 0.9% for ZnO/F127 to 4.2% for ZnO/CTAB at 0.510 mV. A simple procedure for the synthesis of ZnO particles with improved photo(electro)catalytic properties was established and it was found that even a small amount of CTAB used during processing of ZnO increases the surface-to-bulk defect ratio. Optimization of the surface-to-bulk defect ratio in ZnO materials enables increase of the absorption capacity for visible light, rendering of the recombination rate of the photogenerated pair, as well as increase of both the photocurrent density and photoconversion efficiency.

Computational and experimental model of transdermal iontophorethic drug delivery system.

The concept of iontophoresis is often applied to increase the transdermal transport of drugs and other bioactive agents into the skin or other tissues. It is a non-invasive drug delivery method which involves electromigration and electroosmosis in addition to diffusion and is shown to be a viable alternative to conventional administration routs such as oral, hypodermic and intravenous injection. In this study we investigated, experimentally and numerically, in vitro drug delivery of dexamethasone sodium phosphate to porcine skin. Different current densities, delivery durations and drug loads were investigated experimentally and introduced as boundary conditions for numerical simulations. Nernst-Planck equation was used for calculation of active substance flux through equivalent model of homogeneous hydrogel and skin layers. The obtained numerical results were in good agreement with experimental observations. A comprehensive in-silico platform, which includes appropriate numerical tools for fitting, could contribute to iontophoretic drug-delivery devices design and correct dosage and drug clearance profiles as well as to perform much faster in-silico experiments to better determine parameters and performance criteria of iontophoretic drug delivery.

The adsorption of pharmaceutically active compounds from aqueous solutions onto activated carbons.

In this study, the adsorption of pharmaceutically active compounds - salicylic acid, acetylsalicylic acid, atenolol and diclofenac-Na onto activated carbons has been studied. Three different commercial activated carbons, possessing ∼650, 900 or 1500m(2)g(-1) surface areas were used as solid adsorbents. These materials were fully characterized - their textural, surface features and points of zero charge have been determined. The adsorption was studied from aqueous solutions at 303K using batch adsorption experiments and titration microcalorimetry, which was employed in order to obtain the heats evolved as a result of adsorption. The maximal adsorption capacities of investigated solids for all target pharmaceuticals are in the range of 10(-4)molg(-1). The obtained maximal retention capacities are correlated with the textural properties of applied activated carbon. The roles of acid/base features of activated carbons and of molecular structures of adsorbate molecules have been discussed. The obtained results enabled to estimate the possibility to use the activated carbons in the removal of pharmaceuticals by adsorption.

The investigation of phenol removal from aqueous solutions by zeolites as solid adsorbents.

This work reports results on phenol adsorption from aqueous solutions on synthetic BEA (ß) and MFI (ZSM-5) zeolites, studied by heat-flow microcalorimetry. For the sake of comparison, the adsorption was performed on activated carbon, a solid customarily used for removal of phenol from water. The obtained values of heats evolved during phenol adsorption indicate the heterogeneity of active sites present on the investigated systems for the adsorption of phenol. In addition, the amounts of adsorbed pollutant were determined and presented in the form of adsorption isotherms, which were interpreted using Langmuir, Freundlich, Dubinin-Astakov and Sips' equations. The latter was found to express high level of agreement with experimental data. The results obtained in this work reveal that the adsorption of phenol on zeolites depends on both Si/Al ratio and on the pore size. Hydrophobic zeolites that possess higher contents of Si show higher affinities for phenol adsorption. Among investigated zeolites, zeolite ß possesses the highest capacity for adsorption of phenol. The possibility of regeneration of used adsorbents was investigated by thermal desorption technique. It has been shown that in the case of ß zeolite the majority of adsorbed phenol is easily released in the low temperature region.

The adsorption of nicotine from aqueous solutions on different zeolite structures.

The present work is focused on the adsorption of nicotine from aqueous solutions. Based on the data available in the literature, serious concern is claimed regarding the appearance of nicotine in ground, surface and municipal wastewaters. In order to investigate the possibility of abatement by adsorption, three different types of zeolites (BEA, MFI and HEU) have been applied as adsorbents. In addition, the adsorption was performed on activated carbon, a solid customarily used for removal of pollutants from water. The adsorption of nicotine was studied by isothermal microcalorimetry, which provided the heats evolved as a result of adsorption. The values of these heats revealed that the investigated solids are energetically heterogeneous for the adsorption of nicotine from aqueous solution. Additionally, the amounts of adsorbed pollutant were determined and presented in the form of adsorption isotherms. The obtained adsorption isotherms were interpreted using Langmuir, Freundlich, and Sips equations; the latter was found to express high level of agreement with experimental data of nicotine adsorption on the investigated solids. The possibilities to regenerate the adsorbents were examined by means of thermogravimetry coupled with mass spectrometry. From all obtained results, it was possible to distinguish zeolite BEA as a material which possesses the capacity for adsorption of nicotine comparable to that of activated carbon.