The polycondensation of resorcinol and formaldehyde in a water–ethanol mixture using the adapted Stöber method was used to obtain resol resins. An optimization of synthesis conditions and the use of an appropriate stabilizer (e.g., poly(vinyl alcohol)) resulted in spherical grains. The resins were carbonized in the temperature range of 600–1050 °C and then chemically activated in an aqueous HNO3 solution, gaseous ammonia, or by an oxidation–reduction cycle (soaking in a HNO3 solution followed by treatment with NH3). The obtained carbons were characterized by XRD, the low-temperature adsorption of nitrogen, SEM, TGA, and XPS in order to determine degree of graphitization, porosity, shape and size of particles, and surface composition, respectively. Finally, the materials were tested in phenol adsorption. The pseudo-second order model perfectly described the adsorption kinetics. A clear correlation between the micropore volume and the adsorption capacity was found. The content of graphite domains also had a positive effect on the adsorption properties. On the other hand, the presence of heteroatoms, especially oxygen groups, resulted in the clogging of the pores and a decrease in the amount of adsorbed phenol.
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.
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