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Photoactive TiO2 materials based on a C@TiO2 core-shell structure synthesized according to the bottom-up strategy using a spherical resin core were presented in relation to commercial TiO2 (P25) used as a reference material. The studied TiO2 materials were modified with Ag nanoparticles using two alternative methods: impregnation and precipitation. Depending on the deposition technique used, different distributions of the Ag modifier were achieved within the TiO2 structure. As confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements, the precipitation technique resulted in the formation of almost twice smaller, highly dispersed Ag nanoparticles compared to impregnation. Furthermore, the effect of the performed modification on the textural properties (low-temperature N2 adsorption) and surface composition (X-ray photoelectron spectroscopy) was determined. The phase composition of the TiO2 support as well as the dispersion of the Ag modifier significantly affected the energy gap determined from UV–Vis spectra and, consequently, their performance in the process photodegradation of 4-nitrophenol tested as a model molecule. In the case of the @TiO2 material modified with highly dispersed Ag, significantly higher photoactivity in the visible light range was observed than in the presence of analogous P25-based materials.

A wide series of copolymer materials with various contents of 4-vinyl-diisopropyl-phtalate ester (10–90 mol%), divinylbenzene (1–11 mol%) and styrene, as monomers, were obtained by radical copolymerization. In the last steps of the synthesis, diisopropyl ester functionalities were converted into the form of N-hydroxyphthalimide (NHPI) rings. The obtained materials with the NHPI groups immobilized in the copolymer structure were studied by various physicochemical techniques, including FT-IR, UV-Vis-DR, XPS, elemental analysis, and tested as catalysts in aerobic oxidation of p-methoxytoluene in the presence of Co(II) acetate co-catalyst. Conversion of the aromatic substrate was correlated with the NHPI content and cross-linking degree. The best catalytic performance (conversions higher than 23%) was achieved for the copolymer catalysts containing 60% and 30% of 4-vinyl-diisopropyl-phtalate ester. At too high concentrations of NHPI and DVB, some of the NHPI groups were transformed into inactive (C=O)-N=O species or not available due to embedding inside the copolymer structure. The mechanism of the process involving both NHPI centers, forming phthalimide N-oxyl (PINO) radicals, and Co(II) cations was discussed. Stability of the developed catalysts was also tested. The opening of imide rings took place during the catalytic process, resulting in the formation of carboxyl groups and the release of hydroxylamine molecules. The deactivated catalyst could be easily regenerated by repeating two last steps of closing imide ring.

Bearing in mind the need to develop optimal transition metal oxide-based catalysts for the combustion of volatile organic compounds (VOCs), yolk-shell materials were proposed. The constructed composites contained catalytically active Co3O4 nanoparticles, protected against aggregation and highly dispersed in a shell made of porous SiO2, forming a specific type of nanoreactor. The bottom-up synthesis started with obtaining spherical poly(styrene-co-acrylic acid) copolymer (PS30) cores, which were then covered with the SiO2 layer. The Co3O4 active phase was deposited by impregnation using the PS30@SiO2 composite as well as hollow SiO2 spheres with the removed copolymer core. Structure (XRD), morphology (SEM), chemical composition (XRF), state of the active phase (UV-Vis-DR and XPS) and reducibility (H2-TPR) of the obtained catalysts were studied. It was proven that the introduction of Co3O4 nanoparticles into the empty SiO2 spheres resulted in their loose distribution, which facilitated the access of reagents to active sites and, on the other hand, promoted the involvement of lattice oxygen in the catalytic process. As a result, the catalysts obtained in this way showed a very high activity in the combustion of toluene, which significantly exceeded that achieved over a standard silica gel supported Co3O4 catalyst.