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The effect of different water matrices on the photocatalytic degradation of dissolved pharmaceuticals was explored. The focus was on the degradation efficiencies in wastewater effluent from a bioreactor and water effluent from a central wastewater treatment plant and comparing the results with degradation in deionized H$_2$O. The compounds tested included: oxytetracycline, marbofloxacin, ibuprofen, diclofenac, phenytoin, ciprofloxacin, sulfamethoxazole. For the experiments performed in this study, a compact packed-bed photocatalytic reactor was used in which the hybrid TiO$_2$ photocatalyst (sol-gel/P25) was deposited on ∼3 mm glass beads. As expected, the reactions proceed more slowly in wastewater than in deionized water, yet it is shown that removal of the compounds from the water is still possible even when other organic molecules are present. Total organic carbon measurements have shown that complete mineralization takes place albeit at slower rates than the initial degradation of parent compounds. The results show that an acidic pH can increase the reaction rates and the adsorption on the photocatalyst surface. Analyses of the degradation intermediates were performed using tandem liquid chromatography triple-quadrupole mass spectrometry system. Additionally, X-ray absorption spectroscopy was applied to get insight into the local structure of the photocatalyst before and after use. Understanding the effects that different wastewater compositions have on photocatalytic reactions will help to refine the potential applications of the technology.

Soavtorji: Boštjan Žener, Marin Kovačić, Hrvoje Kušić, Iztok Arčon, Marjetka Levstek, Urška Lavrenčič Štangar. Bibliografija: str. 30-39. Abstract.

ACS applied materials & interfaces 14(28), 31862 - 31878 (2022). doi:10.1021/acsami.2c05221, Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H$_2$ and CO (syngas). CeO$_2$ nanorods, nanocubes, and nanospheres were decorated with 1–4 wt % Ni. The materials were structurally characterized using TEM and in situ XANES/EXAFS. The CO$_2$ activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO$_2$ morphologies expose {111} and {100} terminating facets, varying the strength of the CO$_2$ interaction and redox properties, which influence the CO$_2$ activation. Temperature-programmed CO$_2$ DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to H$_2$O and CO. In excess hydrogen, methane is the preferred reaction product. The CeO$_2$ cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria’s surface, resulting in less-abundant surface sites for CO$_2$ dissociation., Published by Soc., Washington, DC

In wheat (Triticum aestivum L.), the awns—the bristle-like structures extending from lemmas—are photosynthetically active. Compared to awned cultivars, awnletted cultivars produce more grains per unit area and per spike, resulting in significant reduction in grain size, but their mineral element composition remains unstudied. Nine awned and 11 awnletted cultivars were grown simultaneously in the field. With no difference in 1000-grain weight, a larger calcium and manganese—but smaller iron (Fe) concentrations—were found in whole grain of awned than in awnletted cultivars. Micro X-ray absorption near edge structure analysis of different tissues of frozen-hydrated grain cross-sections revealed that differences in total Fe concentration were not accompanied by differences in Fe speciation (64% of Fe existed as ferric and 36% as ferrous species) or Fe ligands (53% were phytate and 47% were non-phytate ligands). In contrast, there was a distinct tissue-specificity with pericarp containing the largest proportion (86%) of ferric species and nucellar projection (49%) the smallest. Phytate ligand was predominant in aleurone, scutellum and embryo (72%, 70%, and 56%, respectively), while nucellar projection and pericarp contained only non-phytate ligands. Assuming Fe bioavailability depends on Fe ligands, we conclude that Fe bioavailability from wheat grain is tissue specific.