Sonochemical synthesis of SnS and SnS2 quantum dots from aqueous solutions, and their photo- and sonocatalytic activity.

Our study reports the ultrasound-assisted synthesis of SnS and SnS2 in the form of nanoparticles using aqueous solutions of respective tin chloride and thioacetamide varying sonication time. The presence of both compounds is confirmed by powder X-ray diffraction, energy-dispersive X-ray spectroscopy, as well as Raman and FT-IR spectroscopic techniques. The existence of nanoparticles is proven by powder X-ray diffraction investigation and by high resolution transmission electron microscopy observations. The size of nanocrystallites are in the range of 3-8 nm and 30 50 nm for SnS, and 1.5-10 nm for SnS2. X-ray photoelectron spectroscopy measurements, used to investigate the chemical state of tin and sulphur atoms on the surface of nanoparticles, reveal that they are typically covered with tin on the same oxidation degree as respective bulk compound. Values of optical bandgaps of synthesized nanoparticles, according to the Tauc method, were 2.31, 1.47 and 1.05 eV for SnS (60, 90 and 120 min long synthesis, respectively), and 2.81, 2.78 and 2.70 eV for SnS2 (60, 90 and 120 min long synthesis, respectively). Obtained nanoparticles were utilized as photo- and sonocatalysts in the process of degradation of model azo-dye molecules by UV-C light or ultrasound. Quantum dots of SnS2 obtained under sonication lasting 120 min were the best photocatalyst (66.9 % color removal), while quantum dots of SnS obtained under similar sonication time were the best sonocatalyst (85.2 % color removal).

An introductory laboratory class in sonochemistry.

This article proposes a substantive scope and scenario of a laboratory class that introduces students to the field of sonochemistry. The class requires only basic laboratory equipment - typical laboratory glassware like graduated pipettes and conical flasks, as well as simple inorganic chemicals. It is designed to acquaint students with fundamental aspects of sonochemistry. In the qualitative aspect, they will conduct and observe some sonochemical reactions like a synthesis of hydrogen peroxide and ultrasound-assisted degradation of toxic chromates(VI) which will demonstrate the indirect consequences of water sonolysis which is the most basic sonochemical reaction, as well as they will illustrate the applications of sonochemistry. In the quantitative aspect, students will learn about how to measure the power of ultrasound and the sonochemical efficiency of the reaction and will conduct experiments allowing for the calculation of these parameters. Finally, an introduction to and demonstration of the sonocatalytic effect is planned. An evaluation system, consisting of a report and test, is also proposed.

Dye-Modified, Sonochemically Obtained Nano-SnS2 as an Efficient Photocatalyst for Metanil Yellow Removal.

We investigate the possibility of modification of SnS2 powder through sonochemical synthesis with the addition of an organic ligand. For that purpose, two organic dyes are used, Phenol Red and Anthraquinone Violet. All obtained powders are characterized using XRD, SEM, EDX, FT-IR, and UV-Vis investigations. Synthesized samples showed composition and structural properties typical for sonochemically synthesized SnS2. However, investigation with the Tauc method revealed that SnS2 powder modified with Phenol Red exhibits a significant shift in value of optical bandgap to 2.56 eV, while unmodified SnS2 shows an optical bandgap value of 2.42 eV. The modification of SnS2 powder with Anthraquinone Violet was unsuccessful. The obtained nanopowders were utilized as photocatalysts in the process of Metanil Yellow degradation, revealing that SnS2 modified with Phenol Red shows about 23% better performance than the unmodified one. The mean sonochemical efficiency of the performed synthesis is also estimated as 9.35 µg/W.

Removal of Bromocresol Green from aqueous solution by electro-Fenton and electro-Fenton-like processes with different catalysts: laboratory and kinetic model investigation.

This study presents the removal of triarylmethane dye Bromocresol Green from aqueous solution by the electro-Fenton process. As catalysts five different cations were used: Fe2+, Ce3+, Ni2+, Mn2+, and Co2+. They play crucial roles in the whole process because they react with H2O2 producing hydroxyl radicals that are capable of breaking down dye molecules. Based on this, a comparison of catalytic activity of these cations in the electro-Fenton process is made for Bromocresol Green degradation. A simple and universal kinetic model is also applied to study the catalytic activity of investigated catalysts. Due to its multidimensionality it is fitted to experimental data using a genetic algorithm. The procedure of fitting using a genetic algorithm is thoroughly described and demonstrated. The activity of utilized catalysts is compared based on both experimental and model data revealing that for Bromocresol Green removal all alternative catalysts (Ni2+, Co2+, Ce3+, Mn2+) are better than the typical one (Fe2+, 51.83% degradation). The best catalyst is Co2+ with 78.35% degradation efficiency. Moreover, the adopted kinetic model proved its universality and outlined different interactions between catalysts and dye molecules.

Sonochemical preparation of SnS and SnS2 nano- and micropowders and their characterization.

Sonochemical production of tin(II) and tin(IV) sulfides is investigated. Different conditions of syntheses are examined: used solvent (ethanol or ethylenediamine), source of tin (SnCl2 or SnCl4), the molar ratio of thioacetamide to the tin source, and time of sonication. The obtained powders are characterized by the X-ray diffraction method (PXRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), and the Tauc method. Raman and FT-IR measurements were performed for the obtained samples, which additionally confirmed the crystallinity and phase composition of the samples. The influence of experimental conditions on composition (is it SnS or SnS2), morphology, and on the bandgap of obtained products is elucidated. It was found that longer sonication times favor more crystalline product. Each of bandgaps is direct and most of them show typical values - c.a. 1.3 eV for SnS and 2.4 eV for SnS2. However, there are some exceptions. Synthesized powders show a variety of forms such as needles, flower-like, rods, random agglomerates (SnS2) and balls (SnS). Using ethanol as a solvent led to powders of SnS2 independently of which tin chloride is used. Sonochemistry in ethylenediamine is more diverse: this solvent protects Sn2+ cations from oxidation so mostly SnS is obtained, while SnCl4 does not produce powder of SnS2 but Sn(SO4)2 instead or, at a higher ratio of thioacetamide to SnCl4, green clear mixture.

Application of artificial neural network and global optimization techniques for high throughput modeling of the crystal structure of stannites and kesterites.

This study aims to apply artificial neural networks for the prediction of the lattice parameters of materials with stannite- and kesterite-type structure, and to compare the results of predictions with that obtained in the calculations exploiting the density functional theory. Crystallographic data for 49 compounds with stannite-type structure and for four compounds with the kesterite-type structure are found and, based on it, crystal structures are calculated using the density functional theory (DFT) method in a two-step relaxation procedure for all compounds. An multilayer Perceptron is constructed, which then is trained on gathered crystallographic data. Values predicted by a neural network (lattice parameters) are compared with experimental data and with results of DFT calculations. Moreover, a global optimization method (the Uspex code) is used to find potentially novel crystal structures for investigated chemical compositions. The results are discussed in the term of advantages and disadvantages of each method.

Application of sonochemically synthesized SnS and SnS2 in the electro-Fenton process: Kinetics and enhanced decolorization.

SnS and SnS2 powders were synthesized with the use of ultrasound. The indirect sonication was applied with ultrasound frequency 40 kHz and acoustic power 38 W/L. Products of syntheses were examined with PXRD, TEM, EDX, XPS, and UV-Vis (the Tauc method) investigations. The resulting microparticles were used for tip coating of copper cathodes. These electrodes were used in the degradation of model azo-dye Metanil Yellow by the electro-Fenton process. The efficiencies of degradation using copper, SnS-coated copper, and SnS2-coated copper cathodes are compared. Kinetics of degradation of Metanil Yellow in the electro-Fenton process with the application of three different cathodes is also investigated. It was found that the degradation follows pseudo-first-order and that SnS-coated copper cathode improves the efficiency of degradation, while SnS2-coated copper cathode decreases the efficiency of degradation.

Ti2C MXene Modified with Ceramic Oxide and Noble Metal Nanoparticles: Synthesis, Morphostructural Properties, and High Photocatalytic Activity.

Among two-dimensional (2D) materials, such as graphene, a new family of 2D anisotropic carbides and nitrides of early transition metals (MXenes) is very interesting because of the potential applications in electronics, medicine, and photocatalysis. In this paper, preparation, morphostructural characterization, band gaps determination, and salicylic acid photodegradation ability of Ti2C MXene and six nanocomposites consisting of the MXene modified by TiO2, Ag2O, Ag, PdO, Pd, and Au are reported. It was confirmed using electron diffraction studies, energy dispersive X-ray spectroscopy, and high-resolution transmission microscopy that metals and metal oxides occur on the MXene flakes as nanoparticles in a shape of spots. The band gaps determined experimentally using Tauc's method are placed in the region of 0.90-1.31 eV. In recent years, the method of photocatalytic decomposition of pollutants using semiconductor photocatalysts and UV-vis energy has become increasingly important. The MXene based nanocomposites revealed high activity in the salicylic acid (SA) photodegradation reaction (86.1-97.1% of degraded SA after 3 h, concentration of SA initial solution 100 µM, the circulation rate of the SA solution 0.875 cm3/min). The interfacial charge transfer mechanism and the role of the metallic and metal oxide nanoparticles in the photocatalytic activity of the MXene based nanocomposites are presented and discussed.