This study presents a novel method for the development of TiO2/reduced graphene oxide (rGO) nanocomposites for photocatalytic degradation of dyes in an aqueous solution. The synergistic integration of rGO and TiO2, through the formation of Ti–O–C bonds, offers an interesting opportunity to design photocatalyst nanocomposite materials with the maximum absorption shift to the visible region of the spectra, where photodegradation can be activated not only with UV but also with the visible part of natural solar irradiation. TiO2@rGO nanocomposites with different content of rGO have been self-assembled by the hydrothermal method followed by calcination treatment. The morphological and structural analysis of the synthesized photocatalysts was performed by FTIR, XRD, XPS, UV-Vis DRS, SEM/EDX, and Raman spectroscopy. The effectiveness of the synthesized nanocomposites as photocatalysts was examined through the photodegradation of methylene blue (MB) and rhodamine B (RhB) dye under artificial solar-like radiation. The influence of rGO concentration (5 and 15 wt.%) on TiO2 performance for photodegradation of the different dyes was monitored by UV-Vis spectroscopy. The obtained results showed that the synthesized TiO2@rGO nanocomposites significantly increased the decomposition of RhB and MB compared to the synthesized TiO2 photocatalyst. Furthermore, TiO2@rGO nanocomposite with high contents of rGO (15 wt.%) presented an improved performance in photodegradation of MB (98.1%) and RhB (99.8%) after 120 min of exposition to solar-like radiation. These results could be mainly attributed to the decrease of the bandgap of synthesized TiO2@rGO nanocomposites with the increased contents of rGO. Energy gap (Eg) values of nanocomposites are 2.71 eV and 3.03 eV, when pure TiO2 particles have 3.15 eV. These results show the potential of graphene-based TiO2 nanocomposite to be explored as a highly efficient solar light-driven photocatalyst for water purification.
Manganese-doped ceria nanoparticles were prepared by hydrothermal synthesis and the prepared samples were thermally treated at 500 °C for 2 h. The samples were investigated using x-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), energy-dispersive x-ray spectroscopy (EDS), N2 adsorption and x-ray photoelectron spectroscopy (XPS). XRD revealed that nanocrystalline ceria is the main phase in all samples, while a romanechite-like phase (Na2Mn5O10) appears in the sample doped with 30% of Mn. TEM coupled with EDS exposed the presence of the same phase in the sample doped with 20% Mn. While ceria particles have spherical morphology and particle size ranging from 4.3 to 9.2 nm, the rare crystals of the romanechite-like phase adopt a tubular morphology with a length of at least 1 μm. However, the decrease in the ceria lattice constant and the EDS spectra of the ceria nanoparticles clearly indicate that a substantial amount of manganese entered the ceria crystal lattice. Manganese doping has a beneficial impact on the specific surface area of ceria. XPS measurements reveal a decrease in the Ce3+/Ce3+ + Ce4+ content in the doped samples which is replaced by Mn3+. Moreover, a drastic increase in adsorbed oxygen is observed in the doped samples which is the consequence of the increase in Mn3+ species that promotes oxygen migrations to the surface of the sample. Compared to the pure sample, the doped samples showed significantly higher catalytic activity for the process of toluene oxidation.
Rhabdophane, CePO4∙H2O, nanoparticles were prepared by mechanochemical synthesis with different durations and thoroughly characterized by various characterization techniques. X-ray diffraction analysis showed that the optimal synthesis duration was 15 min, since, in this case, pure rhabdophane is obtained, without traces of contamination by the vessel material. The size of the obtained nanoparticles, as determined from high-resolution transmission electron microscopy images, was around 5 nm. According to UV-Vis diffuse reflectance spectroscopy results, rhabdophane nanoparticles show transparency to visible light and high absorption in the UV region, with a direct bandgap of 3.1 eV. The photocatalytic activity in the Castor oil degradation process and the cytotoxicity for human skin cells were determined and compared to commercial TiO2 nanoparticles, with rhabdophane nanoparticles exhibiting superior properties. Small particle size, purity, absorption in the UV range, transparency to visible light, low photocatalytic activity, and low cytotoxicity indicated the possibility of prepared rhabdophane application as an inorganic UV filter in photoprotective formulations.
The aim of this work was to determine how different types of alkaline pretreatment influence the properties of waste almond and hazelnut nutshell, as well as their compatibility with model inorganic geopolymer matrixes for the formation of biocomposites with potential use in civil engineering. For alkaline pretreatment, 3, 6 and 9% NaOH water solutions and milk of lime were used under different temperature and time conditions. The rise in the crystallinity index was confirmed by X-ray powder diffraction analysis, while the corroboration of the removal of amorphous and undesirable components was demonstrated through Fourier-transform infrared spectroscopy. Furthermore, the effectiveness of the pretreatments was confirmed via simultaneous differential thermal and thermogravimetric analysis, and the positive change in the morphology of the surface of the waste nutshell (WN) and the deposition of the desired phases was established using scanning electron microscopy. Surface free energy and adhesion parameters were calculated using the Owens, Wendt, Rabel and Kaelble method for WN as fillers and geopolymers as model novel inorganic binders. This research indicates that the 6% NaOH treatment is the optimal pretreatment process for preparing WN as the filler in combination with potassium and metakaolin geopolymer that has been cured at room temperature.
Zirconium-doped ceria is a promising and extensively researched catalytic material with notable use in three-way catalytic converters, the oxidation of volatile organic compounds and solid oxide fuel cells. In this work, pure and zirconium-doped ceria nanoparticles (Ce1−xZrxO2, where x = 0, 0.1, 0.2, and 0.3) were prepared by combustion synthesis using glycine as the fuel and cerium and zirconium nitrate as oxidants. The obtained powders were characterized using X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, differential thermal and thermogravimetric analysis, UV–Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The combustion temperature increases with the increase in zirconium content in the samples, but the XRD patterns exclusively show ceria diffraction peaks. The crystallite sizes are in the range from 25.2 to 11.7 nm, and do not vary substantially after thermal treatment, indicating the good thermal stability of the prepared nanocatalysts. XPS analysis showed that the surface amount of zirconium is lower than the nominal and that the ceria sample with 10 mol. % of zirconium has a higher amount of oxygen vacancies than the 30 mol. % Zr-doped sample. The 10 mol. % Zr-doped sample displays the best catalytic activity in the BTEX (benzene, toluene, ethylbenzene, and o-xylene) oxidation process.