In the present study, poly(HEA-co-DVB) was synthesized (loading of OH groups: 8.07 mmol OH/g, crosslinking degree: 6 % DVB) and used for N-hydroxyphthalimide (NHPI) immobilization via ester bond (NHPI loading: 2.06 mmol NHPI/g). The obtained polymeric support and poly(HEA-co-DVB)/NHPI catalyst were characterized by FT-IR and XPS spectroscopy, elemental analysis, thermogravimetry and particle size measurement. The novel polymer-supported NHPI catalyst was tested in aerobic oxidation of p-methoxytoluene and α-methylstyrene. The studied reactions were carried out in the presence of AIBN and/or Co(II) salt without solvent or in acetic acid as solvent. It was found that the obtained polymer-supported NHPI catalyst showed the best catalytic performance, which was attributed to a high content of accessible NHPI moieties. The recovery and recycling of the obtained HEA/DVB-NHPI was only possible in reactions proceeded in solvent-free conditions.
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.
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.
1 January 2022 in Microporous and Mesoporous Materials
In this work, a synthesis and activation path, which enabled the preparation of spherical activated carbon from a lignin precursor, characterized by high adsorption capacity in the removal of phenolic compounds from water, was successfully developed. Two industrial by-products, i.e., Kraft lignin and sodium lignosulfonate, were used to form spherical nanometric lignin grains using pH and solvent shift methods. The obtained materials became precursors to form porous activated carbons via chemical activation (using K2CO3 or ZnCl2 as activating agents) and carbonization (in the temperature range of 600–900 °C). The thermal stabilization step at 250 °C was necessary to ensure the sphericity of the grains during high-temperature heat treatment. The study investigated the influence of the type of chemical activator used, its quantity, and the method of introduction into the lignin precursor, along with the carbonization temperature, on various characteristics including morphology (examined by scanning electron microscopy), the degree of graphitization (evaluated by powder X-ray diffraction), the porosity (assessed using low-temperature N2 adsorption), and the surface composition (analyzed with X-ray photoelectron spectroscopy) of the produced carbons. Finally, the carbon materials were tested as adsorbents for removing phenol from an aqueous solution. A conspicuous impact of microporosity and a degree of graphitization on the performance of the investigated adsorbents was found.