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This study tracked five pharmaceutically active compounds (PhACs) in Mexico City's sewage, namely, famotidine, indomethacin, dexamethasone, azithromycin, and ivermectin, which were used to treat COVID-19. The monitoring campaign was carried out over 30 months (May 2020 to November 2022), covering the five COVID-19 waves in Mexico. In the Central Emitter, the main sewage outflow, famotidine displayed levels of 132.57 ± 28.16 ng L-1 (range from < LOQ to 189.1 ng L-1), followed by indomethacin (average 672.46 ± 116.4 ng L-1, range from 516.7 to 945.2 ng L-1), dexamethasone (average 610.4 ± 225.7 ng L-1, range from 233.4 to 1044.5 ng L-1), azithromycin (average 4436.2 ± 903.6 ng L-1, range from 2873.7 to 5819.6 ng L-1), and ivermectin (average 3413.3 ± 1244.6 ng L-1, range from 1219.8 to 4622.4 ng L-1). The concentrations of dexamethasone, azithromycin and ivermectin were higher in sewage from a temporary COVID-19 care unit, by a factor of 3.48, 3.52 and 2.55, respectively, compared with those found in municipal wastewater. In the effluent of the Atotonilco Wastewater Treatment Plant (AWWTP), which treats near 60 % of the Mexico City's sewage, famotidine was absent, while concentrations of indomethacin, dexamethasone, azithromycin and ivermectin were 78.2 %, 76.7 %, 74.4 %, and 88.1 % lower than those in the influent, respectively. The occurrence of PhACs in treated and untreated wastewater resulted in medium to high environmental risk since Mexico City's wastewater is reused for irrigation in the Mezquital Valley. There, PhACs were found in irrigation canals at lower levels than those observed in Mexico City throughout the monitoring. On the other hand, famotidine, indomethacin, and dexamethasone were not found in surface water resulting from the infiltration of wastewater through soil in Mezquital Valley, while azithromycin and ivermectin sporadically appeared in surface water samples collected through 2021. Using an optimized risk assessment based on a semi-probabilistic approach, the PhACs were prioritized as ivermectin > azithromycin > dexamethasone > famotidine > indomethacin.

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In this work, fern-leaf-like BiVO4 was used to photocatalytically reduce Cr6+ in water. Nanosized BiVO4 displayed bandgap energy and specific surface area of 2.49 eV and 5.65 m2 g-1, respectively. Metallic Au nanoparticles were deposited on the BiVO4 to increase the photocatalytic performance. To optimize the reaction conditions, the sacrificial agents methanol, ethanol, formic acid, dimethyl sulfoxide, and KI were tested, while different catalyst dosages and Au loadings were assessed. The best sacrificial agent was formic acid, which was used at an optimal concentration of 0.01 mol L-1. The complete removal of Cr6+ was attained after 90 min of visible light irradiation using a catalyst dosage of 1.5 g L-1. Depositing metallic Au nanoparticles barely improved the photocatalytic performance, thus unmodified BiVO4 was used to remove Cr6+ in tap water. The matrix effect slowed the photocatalytic process, and the complete removal of Cr6+ was achieved in 120 min. Cr3+ and Cr6+ species were precipitated on the catalyst surface at the end of the photocatalytic process; still, BiVO4 displayed high stability after three reaction cycles.

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The present work highlights the versatility of a TiO2-Al2O3 mixed oxide bearing highly dispersed gold nanoparticles that was applied in the CO oxidation reaction at room temperature. The TiO2, Al2O3, and TiO2-Al2O3 supports were synthesized by the sol-gel method, while gold nanoparticles were added by the deposition-precipitation with urea method using a theoretical Au loading of 2 wt.%. A promotional effect of the TiO2-Al2O3 support on the activity of gold catalysts with respect to TiO2 and Al2O3 was observed; Au/TiO2-Al2O3 showed outstanding CO oxidation, being active from 0 °C and stable throughout a 24-h test. As for the alumina content (5, 10, and 15 wt.%) in TiO2, it improved the textural properties by retarding the crystal growth and anatase-rutile phase transformation of TiO2, suppressing the deposition of carbon on the catalyst surface and stabilizing the Au nanoparticles even at high temperatures. Gold was highly dispersed with nanoparticle sizes ranging from 1 to 2 nm when H2 was used to treat thermally the Au/TiO2-Al2O3, Au/TiO2, and Au/Al2O3 materials. In addition, the XPS technique helped elicit that Au0 and Au1+ boosted their interaction with the TiO2, Al2O3, and TiO2-Al2O3 supports by means of charge transfer, which resulted in outstanding CO oxidation activity from 0 °C. Likewise, the key factors that control the peculiar catalytic performance in the CO oxidation reaction are discussed, which represents a step forward in the versatility behavior of gold catalysts supported on mixed oxide catalysts.

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A density functional theory + U systematic theoretical study was performed on the geometry, electronic structure, and energies of properties relevant for the chemical reactivity of TiO2 anatase. The effects of D3(BJ) dispersion correction and the Hubbard U value over the energies corresponding to the TiO2/Ti2O3 reduction reaction, the oxygen vacancy formation, and transition-metal doping were analyzed to attain an accurate and well-balanced description of these properties. It is suggested to fit the Hubbard correction for the metal dopant atom by taking as reference the observed low spin-high spin (HS) energy difference for the metal atom. PBEsol-D3 calculations revealed a distinct electronic ground state for the yttrium-doped TiO2 anatase surface depending upon the type of doping and interstitial or substitutional defects. Based on the calculations, it was found that a HS state explains the observed ferromagnetism in cobalt-substituted TiO2 anatase. The results presented herein might be relevant for further catalytic studies on TiO2 anatase using a large surface model that would be worthwhile for heterogeneous catalysis simulations.

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Low-temperature CO oxidation was carried out by using rhodium incorporated into titanate nanotubes (Rh/NTs) prepared by the sol-gel and hydrothermal methods; otherwise, gold nanoparticles were deposited homogeneously onto the Rh/NT surface through the deposition-precipitation with urea (DPU) method. The Au-Rh/NT sample exhibited high metal dispersion (55%), outstanding CO oxidation at low temperature, and better resistance to deactivation than the monometallic Rh/NT and Au/NT samples. The characterization of bimetallic samples, with particle sizes from 1 to 3 nm, revealed the remarkable presence of interacting Au and Rh species in metallic state. In this way, Au0 and Rh0 were answerable for the higher catalytic activity observed in the bimetallic samples. The interaction between Au and Rh in the nanoparticles of Au-Rh/NT promoted a synergistic effect on the CO oxidation reaction, explained by the creation of new CO adsorption sites.

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In this study, the magnetic fraction (MF) of a low-grade titanium ore (TO) was successfully used as an alternative Fe2+ source in five reuse cycles, in combination with persulfate (PS) and simulated sunlight (SSL) for the degradation of ciprofloxacin (CIP). The best response of the CIP initial concentration, irradiation time, and doses of MF and PS to degrade completely this pollutant were determined based on an experimental design. However, the individual application of MF, PS, or SSL fails to achieve this goal at the optimal experimental condition. Furthermore, the MF-PS-SSL system showed a higher production of sulfate radicals and a concentration of dissolved Fe2+ ions compared with data obtained for the MF-PS system. The best performance attained by the former system is due to the synergy produced between the photo-generated electrons, and the reaction of PS with the Fe2+ ions leached gradually from the MF, which increased sulfate radical production. After five reuse cycles of the MF, the oxidation system showed a CIP degradation of 100% in 100 min, no residual content of PS, a CIP mineralization of 6%, a marginal increase in the biodegradability (BOD5/COD ratio), a MF loss of 7.5%, and a twofold increase in toxicity; however, this parameter was lower than the effective concentration at 50% inhibition (EC50). The substitution of MF with an iron salt decreased the degradation efficiency of the antibiotic by 14%, probably owing to the immediate excess of Fe2+ in the solution, which can be oxidized to Fe3+ ions, and as a consequence of this, the production rate of the sulfate radical was also reduced.

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Mono- (Au, Ag and Cu) and bi-metallic (Au-Ag and Au-Cu) nanoparticles were deposited on TiO2 and tested for the photocatalytic degradation of sulfamethoxazole using either UV-C or simulated sunlight. The optimal loading of metallic nanoparticles was determined as 1.5 wt% for Au and Ag, and 1.0 wt% for Cu. In the case of bi-metallic nanoparticles, only the ratio 1:0.5 wt% for both Au-Ag and Au-Cu was tested. In experiments using UV-C light, the highest degradation performance was found for Ag/TiO2, while bi-metallic nanoparticles supported on TiO2 also showed increased photocatalytic activity compared with unmodified TiO2. In simulated sunlight irradiation tests, Au/TiO2 showed to be the most efficient material. Complete mineralization of sulfamethoxazole was achieved when surface-modified materials were tested in both UV-C and simulated sunlight experiments. Photolysis was efficient to fully degrade sulfamethoxazole, although mineralization was lower than 10% for both luminic sources. The main by-products of sulfamethoxazole were determined in photolysis and photocatalysis tests using UV-C light, and degradation paths were proposed. By-products showed non-toxicity and low antibiotic activity. Reuse of the catalysts upon three reaction cycles did not result in the loss of activity.

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The nature and size of the real active species of nanoparticulated metal supported catalysts is still an unresolved question. The technique of choice to measure particle sizes at the nanoscale, HRTEM, has a practical limit of 1 nm. This work is aimed to identify the catalytic role of subnanometer species and methods to detect and characterize them. In this frame, we investigated the sensitivity to redox pretreatments of Ag/Fe/TiO2, Ag/Mg/TiO2 and Ag/Ce/TiO2 catalysts in CO oxidation. The joint application of HRTEM, SR-XRD, DRS, XPS, EXAFS and XANES methods indicated that most of the silver in all samples is in the form of Ag species with size <1 nm. The differences in catalytic properties and sensitivity to pretreatments, observed for the studied Ag catalysts, could not be explained taking into account only the Ag particles whose size distribution is measured by HRTEM, but may be explained by the presence of the subnanometer Ag species, undetectable by HRTEM, and their interaction with supports. This result highlights their role as active species and the need to take them into account to understand integrally the catalysis by supported nanometals.

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The effect of Au, Ag, Cu and Ni nanoparticles deposited on TiO2-P25 was studied on the photodegradation of trimethoprim, a commonly used antibiotic. The synthesized materials were characterized by ICP, EDS, XRD, BET, UV-vis, TEM and TPR. The metal loading was 0.5 wt.% and the average particle size was about 2 nm in all the studied samples. The deposition of metallic particles on TiO2-P25 produces an enhancement of the activity of the bare semiconductor; when the degradation of trimethoprim was carried out by pure TiO2-P25, the mineralization reached only 50% of the organic matter, while by using metallic nanoparticles deposited on TiO2-P25, the mineralization of organic matter increased up to 80% for the same reaction conditions and reaction time. The evaluation of the photocatalytic activity was made for solutions containing trimethoprim in concentrations of 40 ppm under UV light irradiation using a lamp with primary emission at 254 nm and 2.2 mW/cm(2). It is shown that the ability of the photocatalyst to mineralize trimethoprim depends on the electron affinity and the electronegativity of the deposited metal.

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Gold nanoparticles were deposited on the surface of multiwalled carbon nanotubes (MWNTs) functionalized with aliphatic bifunctional thiols (1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, and 2-aminoethanethiol) through a direct solvent-free procedure. Small gold particles, with a narrow particle size distribution around 1.7 nm, were obtained on 1,6-hexanedithiol-functionalized MWNTs. For MWNTs functionalized with the aminothiol, the average Au particle size was larger, 5.5 nm, apparently due to a coalescence phenomenon. Gatan image filter (GIF) observations show that sulfur is at the nanotube surface with a non-homogeneous distribution. A higher sulfur concentration was observed around the gold nanoparticles' location.