Coumarin-based quantification of hydroxyl radicals and other reactive species generated on excited nitrogen-doped TiO2

In order to extend the photoactivity of titanium dioxide into the visible region, highly porous nitrogen-doped TiO2 catalysts (NTiO2) were successfully synthesized by a modified co-precipitation method with ammonium hydroxide as a nitrogen source. Different approaches such as dosing order of the reagents and temperature of the synthesis, calcination period and temperature were tested to examine the optimum outcome regarding photocatalytic OH radical formation under UV and visible light. Coumarin as a traditional probe for this purpose was applied; measuring the luminescence of 7-hydroxycoumarin produced in the reaction with OH radicals, beside the formation of other hydroxylated derivatives. Only a few percentages of the coumarin molecules reacted with OH radicals, while most of them underwent reactions with other photogenerated species such as electrons (anaerobic/aerobic) and superoxide anion radicals (aerobic). Accordingly, our observations suggest that coumarin can also be used as a probe to quantify the formation of other reactive species. The results were obtained from the difference between the amounts of degraded coumarin and hydroxylated coumarin derivatives formed during photocatalytic experiments. These coumarin-based quantifications of photoactivity was applied for the characterization of the prepared nitrogen-doped TiO2 catalysts (NTiO2). In addition, material analysis (X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, and Fourier transform infrared spectroscopy) showed that crystallinity and nitrogen content were found to be crucial features in the photocatalytic performance of the catalysts

Halloysite-Zinc Oxide Nanocomposites as Potential Photocatalysts

The synthesis and structural characterization of synthetic zinc oxide and halloysite-based zinc oxide nanocomposites (with 2–28 m/m% ZnO content) are presented. The chemical precipitation of zinc hydroxide precursors and its subsequent drying at 80 °C yielded dominantly zinc oxide (zincite). Thermal treatment at 350 °C completely transformed the remaining precursor to ZnO without causing structural dehydroxylation of the halloysite support. The procedure yielded zinc oxide nanoparticles with 10–22 nm average size having quasi-spherical scale-like morphology. The specific surface area of the synthetic zinc oxide was found to be low (13 m2/g), which was significantly enhanced after nanocomposite preparation (27–47 m2/g). The photocatalytic activity of the prepared nanocomposites was probed by the degradation of a phenolic compound (4-nitrophenol) upon UV irradiation in liquid phase. Compared to their individual constituents, an increased activity of the nanocomposites was observed, while the SSA-normalized photocatalytic activity revealed a synergic effect in nanocomposites above 9 m/m% ZnO content. The nanocomposites were found to be stable at pH = 5.6, with a minor and major mobilization of zinc ions at pH = 12.4 and pH = 1.9, respectively. The toxicity of leachates in different pH environments by Vibrio fischeri bioluminescence indicated low toxicity for ZnO nanoparticles and insignificant toxicity for the nanocomposites. The enhanced photocatalytic activity together with the lower toxicity of the halloysite-ZnO nanocomposites highlight their application potential in water treatment

Kaolins of high iron-content as photocatalysts: Challenges of acidic surface modifications and mechanistic insights

Surface modifications of natural kaolins (Felsőpetény, Hungary) with iron-content up to 9% (m/m) were carried out by varying acid concentration (5, 8 and 11 M HCl) and treatment time (1, 3 and 6 h) in order to evaluate the influence of treatment conditions on photochemical activity, amount of low coordinate Al defect sites, porosity, and acid/base character of the surface. Nitrogen adsorption and temperature-programmed desorption measurements showed that the acid treatment slightly reduced the pore volume and the surface area, while the average pore diameter and the number of acidic centers were increased. Solid-state 27Al NMR spectroscopy demonstrated the presence of mechanistically relevant Al defect sites. The distribution, concentration, and particle size of the iron oxide co-minerals were found to be influential to photochemical activity. Greater than 90% photochemical degradation efficiency of oxalic acid can be achieved by acid-treated samples upon 3 h exposure to 8 M HCl solution with good reproducibility

Removal of Methylene Blue from Aqueous Solution by Mixture of Reused Silica Gel Desiccant and Natural Sand or Eggshell Waste

The purpose of this work was to develop, characterize and test new low-cost materials suitable for removing methylene blue dye from water and wastewater by adsorption. The solid materials consisted of silica gel powder (SG), silica gel mixed with eggshell powder (SG-ES) and a mixture of silica gel with sand from the western Iraqi desert (SG-SI). The samples were milled by using an electrical mixer and a ball mill, followed by a drying step. In addition, desert sand was acid-treated in order to remove impurities. The structure and chemical composition of the samples were investigated by X-ray diffraction (XRD), a scanning electron microscopy technique equipped with an energy-dispersive X-ray spectrometer (SEM-EDX), a low-temperature nitrogen adsorption (BET) technique, thermo-analytical (TG/TGA) measurements and Fourier-transformed infrared spectroscopy (FTIR). The previously mentioned materials were tested to remove methylene blue from an aqueous solution. The adsorption experiments were monitored by ultraviolet–visible (UV-Vis) spectrophotometry and showed that SG and SG-ES gave promising results for the methylene blue removal from water. After 40 min of treatment of the aqueous solution containing 10 mg/L of MB at room temperature, the tested SG, SG-ES and SG-SI materials were found to have 86%, 80% and 57% dye adsorption efficiency, respectively. Taking into consideration not only the adsorption activity of the studied material but their availability, cost and concepts of cleaner production and waste minimization, the developed silica gel with eggshell can be considered as a good, cost-effective alternative to commercially available activated-carbon-based adsorbents. Different kinetic and isotherm models were fitted to the experimental results. A pseudo-second-kinetics-order model revealed high correlation fitting, while the Freundlich model was found to appropriately describe the adsorption isotherm. The thermal stability during the possible regeneration process of the SG-ES adsorbent mixture and its interaction mechanism with cationic dye was discussed

Novel Hybrid Nanoparticles: Synthesis, Functionalization, Characterization, and Their Application in the Uptake of Scandium (III)Ions from Aqueous Media

The aim of this study was to prepare novel supramolecular hybrid nanoparticles (HNPs) that can selectively separate and recover scandium metal ions, Sc(III), from an aqueous phase based on molecular recognition technology (MRT). Moreover, this approach is fully compatible with green chemistry principles. In this work, natural amorphous silica (SiO2) nanoparticles were prepared by a precipitation method from Iraqi rice husk (RH) followed by surface modification with 3-amino-propyl triethoxysilane (APTES) as coupling agent and Kryptofix 2.2.2 (K2.2.2) as polycyclic ligand. To evaluate the potential of the hybrid nanoparticles, the prepared HNPs were used for the solid–liquid extraction of scandium, Sc(III), ions from model solutions due to the fact that K2.2.2 are polycyclic molecules. These polycyclic molecules are able to encapsulate cations according to the corresponding cavity size with the ionic radius of metal by providing a higher protection due their cage-like structures. Moreover, the authors set the objectives to design a high-technology process using these HNPs and to develop a Sc recovery method from the aqueous model solution prior to employing it in industrial applications, e.g., for Sc recovery from red mud leachate. The concentrations of Sc model solutions were investigated using the UV-Vis spectrophotometer technique. Different characterization techniques were used including scanning electron microscope (SEM), atomic force microscopy (AFM), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), X-ray fluorescence (XRF), and Fourier transform infrared (FTIR). The extraction efficiency of Sc varied from 81.3% to 96.7%. Moreover, the complexed Sc ions were efficiently recovered by HCl with 0.1 mol/L concentration. The stripping ratios of Sc obtained ranged from 93.1% to 97.8%