Facultad Regional Buenos Aires
Permanent URI for this communityhttp://48.217.138.120/handle/20.500.12272/6
Browse
6 results
Search Results
Item Preliminary results of photocatalytic Cr(VI) reduction using TiO2 films grown by cathodic arc deposition: effect of the film thickness and the N-doping(2023-06-08) Kleiman, Ariel; Meichtry, Jorge Martín; Xaubet, M.; Grondona, D.; Litter, Marta Irene; Márquez, AdrianaTiO2 is the most studied photocatalyst for the treatment of pollutants; however, its rather large band gap and the need for a removal step when used as a suspension hinder the wide application of this technology. Immobilized TiO2 films grown by cathodic arc deposition (CAD) have shown superior adhesion to the substrate and activities similar to that of P-25 TiO2 films, the reference photocatalyst, but they still require UV light to be excited [1]. N-doping is a strategy frequently used to extend the TiO2 band gap to the visible range [2], but it has a scarce application on CAD-grown films. In this work, TiO2 CAD films, with and without N-doping, were prepared and tested on the photocatalytic removal of Cr(VI), a priority water pollutant, in the presence of ethylenediaminetetraacetic acid (EDTA) as an organic donor. TiO2 films of different thicknesses: (290 ± 40 nm), (440 ± 40) nm, and (850 ± 70) nm, were deposited by CAD according to a reported method [1]. The doping of the films was performed by plasma immersion ion implantation in a N2 environment. For comparison, P-25 TiO2 films of (280 ± 20) nm and (480 ± 30) nm thicknesses were prepared by dip-coating; thicker P-25 films were not stable. All films were grown over a borosilicate glass substrate. Photocatalytic experiments were performed in thermostatted cylindrical glass cells (T = 25 °C) magnetically stirred and irradiated from the top with a HPA 400S lamp (λ > 320 nm, mean UV irradiance 28 W m-2), equipped with an IR filter. 10 mL of a 0.8 mM Cr(VI) and 1 mM EDTA solution at pH 2 (HClO4) were poured into each cell, and 0.25 mL samples were periodically taken for Cr(VI) quantification by the diphenylcarbazide method; at the end of the experiments, a Cr(III)-EDTA complex in solution was determined by direct spectrophotometry [1]. After 5 h of irradiation, Cr(VI) removals of 58% and 85% were obtained with pure and N-doped 290 nm CAD films, respectively, while for pure and N-doped 440 nm CAD films the corresponding removals were 70% and 85%; with the 280 nm and 480 nm P-25 films, Cr(VI) removals were 81% and 88%, respectively. Although thicker CAD films were more efficient (99% of Cr(VI) removal with 850 nm films), no difference could be appreciated between N-doped and undoped films. Cr(VI) evolution could be adjusted to a pseudo-first-order kinetics. In all cases, Cr(III)-EDTA represented 75% of the reduced Cr(VI), the remaining Cr(III) being retained on the TiO2 surface, [1]. The photocatalytic efficiency increased with the thickness of the films. Although P-25 films showed a higher photoactivity than the CAD films of similar thickness, thicker and more active CAD films can be surely obtained in future works. N-doping increased slightly the photocatalytic activity of the thinnest films.Item Synergetic combination of nano zero-valent iron, ultrasound and carboxylic acids for the removal of aqueous Cr(VI)(2023-06-08) Cancelada, Lucía; Meichtry, Jorge Martín; Destaillats, Hugo; Litter, Marta IreneCr(VI) is a priority pollutant present in wastewater of several industrial processes such as electroplating and leather tanning; it can be also naturally present in groundwater. The usual treatment of Cr(VI) involves its reduction to Cr(III), a far less toxic and mobile species, which can be precipitated from the solution at circumneutral pH values [1]. However, conventional Cr(VI) chemical reductants, such as Fe(II) salts, require large Fe:Cr molar ratios to be efficient, generating the disposal of large amounts of dangerous sludge. Thus, more efficient Cr(VI) reduction treatments are required. In this work, the efficiency of commercial zero-valent iron nanoparticles (nZVI), ultrasound (US), and carboxylic acids (CAs) for Cr(VI) reduction was evaluated. The CAs used were citric acid (Cit) or ethylenediaminetetraacetic acid (EDTA). The experiments were performed with 200 mL of a 0.3 mM Cr(VI) solution at pH 3 and under air bubbling (0.5 L min-1) at 30 °C for 180 min in an ultrasonic reactor (850 kHz, total power input 35 W L-1). NSTAR (Nanoiron®) was used as nZVI, with a 3:1 Fe:Cr molar ratio (the optimal ratio as determined before for N25 nZVI [2]), Cit (0 or 2 mM) or EDTA (0 or 1 mM). In the absence of Cit or EDTA (nZVI alone or nZVI + US), or with Cit or EDTA alone (neither nZVI nor US), Cr(VI) reduction was negligible (≤ 5% of the initial [Cr(VI)]). US + Cit showed a reduction of 49% of the initial [Cr(VI)], while US + EDTA showed a 32% of reduction. On the other hand, nZVI + US + Cit yielded an 88% of Cr(VI) reduction, which was 60% with nZVI + US + EDTA. This indicates a clear synergy within the ternary system (nZVI + US + CAs). In all cases, the evolution of Cr(VI) could be fitted to a zero-order kinetic model , with R2 values higher than 0.94. NSTAR nZVI particles are composed of a zerovalent Fe core surrounded by a protective shield of iron oxides that inhibits Cr(VI) reduction; thus, only the combination of US and CAs can remove this protective shield and enhance Cr(VI) reduction, being Cit more efficient than EDTA. This was reinforced by the monitoring of the evolution of the total Fe concentration in solution, with final values of 0.076, 0.26, and 0.18 mM for the systems nZVI + US, nZVI + US + Cit and nZVI + US + EDTA, respectively, indicating that Cit and EDTA promote the formation of soluble Fe complexes. Besides, in the previous experiments of US without nZVI, Cit also proved to be a better donor than EDTA, probably because it can stabilize to a higher extent intermediate peroxo-Cr(V) compounds [1]. Summarizing, there is a synergy for Cr(VI) reduction in the ternary system nZVI + US + CAs, being Cit more efficient than EDTA.Item New insights on the UV/TiO2 photocatalytic treatment of thiomersal and its 2-sulfobenzoic acid product(2021-06-28) de la Fourniere, Emmanuel; Meichtry, Jorge Martín; Gautier, Eduardo Amilcar; Custo, Graciela; Litter, Marta IreneAbstract: Background: Thiomersal (TM), a complex between 2-mercaptobenzoic acid (2-MBA) and ethylmercury (C2H5Hg+), is an antimicrobial preservative used in immunological, ophthalmic, cosmetic products, and vaccines. Objective: TM has been treated by UV/TiO2 photocatalysis in the presence or absence of oxygen at acidic pH. C2H5Hg+, 2-MBA, and 2-sulfobenzoic acid (2-SBA) were found as products. A 2-SBA photocatalytic treatment was undertaken to study sulfur evolution. Methods: Photocatalytic runs were performed using a UVA lamp (λmax = 352 nm), open to air or under N2. A suspension of the corresponding TM or 2-SBA salt and TiO2 was prepared, and pH was adjusted. Suspensions were stirred in the dark for 30 min and then irradiated. TM, 2-MBA, 2-SBA, and C2H5Hg+ were quantified by HPLC, sulfur by TXRF, and the deposits on the photocatalyst were analyzed by chemical reactions. The mineralization degree was followed by TOC. Sulfate was determined using BaCl2 at 580 nm. Results: Photocatalytic destruction of TM and total C2H5Hg+ was complete under N2 and air, but TM degradation was much faster in air. The evolution of TM and the products followed a pseudo-first order kinetics. Conclusion: TiO2-photocatalytic degradation is a suitable technique for the treatment of TM and its degradation products. In contrast to other organomercurial compounds, TM degradation is faster in the presence of O2, indicating that the oxidative mechanism is the preferred pathway. A significant TM mineralization (> 60%, NPOC and total S) was obtained. TM was more easily degraded than 2-SBA. Sulfate was the final productItem Treatment of ethylmercury chloride by heterogeneous photocatalysis over TiO2(2021-04-15) de la Fourniere, Emmanuel; Meichtry, Jorge Martín; Gautier, Eduardo Amilcar; Leyva, Ana Gabriela; Litter, Marta IreneEthylmercury chloride (C2H5HgCl) was treated by UV/TiO2 photocatalysis in the presence of O2 and under N2 at pH 4.2. No report exists on C2H5Hg+ degradation by heterogeneous photocatalysis. The adsorption of C2H5Hg+ over TiO2 (no irradiation) was studied and fitted to the Freundlich isotherm. The photocatalytic evolution of C2H5Hg+ was adjusted to a two parameter Langmuir-Hinshelwood model, modified to include a third parameter attributed to the deactivation caused by the deposition of Hg(0). Hg(II) in solution, Hg(0) and Hg2Cl2 (detected only under N2) were the products of the photocatalytic degradation; the organic moiety was degraded but no organic by-product could be detected. Experiments in the absence of O2 showed a higher conversion rate, indicating that C2H5Hg+ is removed both by oxidative and reductive pathways, being this last step partially inhibited by O2. A degradation mechanism considering both oxidative and reductive one-electron transfer steps is proposed.Item Effect of different gases on the sonochemical Cr(VI) reduction in the presence of citric acid(2020-12-01) Meichtry, Jorge Martín; Cancelada, Lucía; Destaillats, Hugo; Litter, Marta IreneThe sonochemical (850 kHz) Cr(VI) reduction (0.30 mM, pH 2) in the presence of citric acid (Cit, 2 mM) was analyzed under different working atmospheres: reactor open to air without sparging (ROAWS), and Ar, O2, air and N2 sparging. Hydrogen peroxide formation in pure water at pH 2 and KI dosimetry were also measured. Zero-order kinetics was observed in all cases. A complete Cr(VI) reduction after 180 min insonation was obtained with the ROAWS and under Ar, while a lower Cr(VI) reduction efficiency was achieved under the other conditions. The Cr(VI) reduction and H2O2 formation rates followed the order ROAWS ?° Ar > air ?° O2 >> N2, while for KI dosimetry the order was ROAWS >> O2 ?° air > Ar >> N2. This indicates that H2O2 formation rate is a better measure of the system reactivity for Cr(VI) reduction. For air, O2 and N2, once the sparging was stopped, Cr(VI) reduction rate increased up to approximately the same value obtained for the ROAWS, suggesting that the sparging decreased the generation of reactive species and, thus, the Cr(VI) reduction rate. Nitrate production was measured at low concentrations (micromolar range) in the ROAWS, air and N2 systems. Formic and acetic acids were detected as Cit degradation products. Reaction mechanisms were proposed. It can be concluded that the best conditions for Cr(VI) removal are with the ROAWS because of a higher Cr(VI) reduction rate, no atmosphere control is required, and it is a less expensive system.Item Photocatalytic activity of TiO2 films prepared by cathodic arc deposition: dependence on thickness and reuse of the photocatalysts(2020-01-25) Meichtry, Jorge Martín; Vega, Daniel; Kleiman, Ariel; Litter, Marta Irene; Márquez, AdrianaIn this work, the photocatalytic activity of anatase films with thicknesses up to 1100 nm prepared by cathodic arc deposition (CAD) on glass substrates is reported. The photocatalytic activity under UV?Vis irradiation (λ > 330 nm) was evaluated through the efficiency in the reduction of 0.80 mM Cr(VI) in the presence of 1 mM ethylenediaminetetraacetic acid (EDTA) at pH 2, and compared with the performance of samples obtained by dip-coating using commercial P25. The CAD films were optically transparent, with visible light transmittance ≥ 50% even for the thickest samples. The photocatalytic efficiency of the films increased as the thickness increased. The possibility of obtaining thicker films allowed cathodic arc films reaching better performance than P25 samples. For the most active films obtained by CAD, complete Cr(VI) reduction could be obtained in <300 min under a 28 W m−2 UV-A irradiance. The photocatalytic reaction for all the studied TiO2 films obeyed pseudo-first order kinetics. A decrease of the reaction rate constant was observed for both types of films after reusing the photocatalysts. The fate of the reduced Cr(VI) was also analyzed.