Advances in Inorganic Mechanochemistry for Applications in Materials Science

γ-Alumina with incorporated metal oxide species (including Fe, Cu, Zn, Bi, and Ga) was synthesized by liquid-assisted grinding—mechanochemical synthesis, applying boehmite as the alumina precursor and suitable metal salts. Various contents of metal elements (5 wt.%, 10 wt.%, and 20 wt.%) were used to tune the composition of the resulting hybrid materials. The different milling time was tested to find the most suitable procedure that allowed the preparation of porous alumina incorporated with selected metal oxide species. The block copolymer, Pluronic P123, was used as a pore-generating agent. Commercial γ−alumina (S_BET = 96 m²·g⁻¹), and the sample fabricated after two hours of initial grinding of boehmite (S_BET = 266 m²·g⁻¹), were used as references. Analysis of another sample of γ-alumina prepared within 3 h of one-pot milling revealed a higher surface area (S_BET = 320 m²·g⁻¹) that did not increase with a further increase in the milling time. So, three hours of grinding time were set as optimal for this material. The synthesized samples were characterized by low-temperature N₂ sorption, TGA/DTG, XRD, TEM, EDX, elemental mapping, and XRF techniques. The higher loading of metal oxide into the alumina structure was confirmed by the higher intensity of the XRF peaks. Samples synthesized with the lowest metal oxide content (5 wt.%) were tested for selective catalytic reduction of NO with NH₃ (NH₃-SCR). Among all tested samples, besides pristine Al₂O₃ and alumina incorporated with gallium oxide, the increase in reaction temperature accelerated the NO conversion. The highest NO conversion rate was observed for Fe₂O₃-incorporated alumina (70%) at 450 °C and CuO-incorporated alumina (71%) at 300 °C. The CO₂ capture was also studied for synthesized samples and the sample of alumina with incorporated Bi₂O₃ (10 wt.%) gave the best result (1.16 mmol·g⁻¹) at 25 °C, while alumina alone could adsorb only 0.85 mmol·g⁻¹ of CO₂. Furthermore, the synthesized samples were tested for antimicrobial properties and found to be quite active against Gram-negative bacteria, P. aeruginosa (PA). The measured Minimum Inhibitory Concentration (MIC) values for the alumina samples with incorporated Fe, Cu, and Bi oxide (10 wt.%) were found to be 4 µg·mL⁻¹, while 8 µg·mL⁻¹ was obtained for pure alumina. Full article

Nickel mono- (NiSe) and diselenide (NiSe₂) were produced from stoichiometric mixtures of powdered Ni and Se precursors by the one-step, undemanding mechanochemical reactions. The process was carried out by high-energy milling for 30 and 120 min in a planetary ball mill. The kinetics of the reactions were documented, and the products were studied in terms of their crystal structure, morphology, electrical, and optical properties. X-ray powder diffraction confirmed that NiSe has hexagonal and NiSe₂ cubic crystal structure with an average crystallite size of 10.5 nm for NiSe and 13.3 nm for NiSe₂. Their physical properties were characterized by the specific surface area measurements and particle size distribution analysis. Transmission electron microscopy showed that the prepared materials contain nanoparticles of irregular shape, which are agglomerated into clusters of about 1–2 μm in diameter. The first original values of electrical conductivity, resistivity, and sheet resistance of nickel selenides synthesized by milling were measured. The obtained bandgap energy values determined using UV–Vis spectroscopy confirmed their potential use in photovoltaics. Photoluminescence spectroscopy revealed weak luminescence activity of the materials. Such synthesis of nickel selenides can easily be carried out on a large scale by milling in an industrial mill, as was verified earlier for copper selenide synthesis. Full article

Mechanochemistry is a method that can cover the energy demand of reaction pathways between solid materials. This requires enough energy to maintain the reactions between the starting materials. This is called “high-energy milling”. In our case, a planetary ball mill provided the required energy. Using the Burgio-equation, the required energy is determinable; the energy released during a single impact of a milling ball (E_b), as well as during the whole milling process (E_cum). The aim of this work was the one-step production of BaTiO₃ from BaO and TiO₂ starting materials. Whereas during mechanochemical reactions it is possible to produce nanoparticles of up to 10 nm, the essence of this study is to develop the preparation of BaTiO₃ with a perovskite structure even without subsequent heat treatment, since sintering at high temperatures is associated with a rapid increase in the size of the particles. By describing the synthesis parameters and their energy values (E_b and E_cum), it is possible to transpose experimental conditions, so that in the case of other types of planetary ball mills or grinding vessel made of other materials, the results can be used. In this study, the mechanical treatment was carried out with a Fritsch Pulverisette-6 planetary ball mill and the transformation of the starting materials was investigated by X-ray diffractometric, Raman and Energy-dispersive X-ray spectroscopic, and transmission electron microscopic measurements. Full article