This work aims to present experimental results on the treatment of methylene blue contaminated wa... more This work aims to present experimental results on the treatment of methylene blue contaminated waters using heterogeneous catalytic ozonation promoted by volcanic sand. The effect of pH (2–8), and the presence of radical scavengers (acetate ions) in homogeneous and heterogeneous systems are evaluated at laboratory scale. Heterogeneous catalytic ozonation using volcanic sand increases methylene blue removal rate. In the presence of free radical scavengers, only a 37% reduction on methylene blue removal rate is observed in the heterogeneous system, as compared with 70% when homogeneous ozonation is used. The results obtained here indicate the importance of chemical surface properties on methylene blue oxidation reactions, suggesting that acid surface sites of volcanic sand play a key role on the reaction mechanism.
In this article, the role of surface sites of modified zeolites with semiconductor nanoparticles ... more In this article, the role of surface sites of modified zeolites with semiconductor nanoparticles as alternative photocatalyts for protecting post-harvest foodstuff from the detrimental effects of ethylene is addressed. Two single and one double catalyst based on zinc and copper oxides supported over modified zeolite samples were prepared. Physical, chemical, and surface properties of prepared materials were studied by several characterization methods. UV-Vis absorption spectra show that the applied modification procedures increase the optical absorption of light in the UV and visible regions, suggesting that an increase in the photocatalytic activity could take place mainly in the obtained co-impregnated catalyst. An ethylene conversion around 50% was achieved when the parent natural zeolite support was modified with both transition metal oxides, obtaining higher removal efficiency in comparison to single oxide catalysts. Adsorption and photocatalytic oxidation experiments were also...
Tomatoes (Solanum lycopersicum L.) are widely cultivated and consumed, but ripening should be car... more Tomatoes (Solanum lycopersicum L.) are widely cultivated and consumed, but ripening should be carried out in controlled storage conditions to extend their shelf life and avoid economic losses. The aim of this study was to investigate the effects of visible artificial light on the ripening and quality of fresh market tomatoes stored at a low temperature and high humidity. The postharvest performance with respect to the ripening of organically grown tomatoes in the Toscano cultivar, with a long storage life, was studied in the presence and the absence of visible LED light. The maturation kinetics of the tomatoes was modeled using the Power Law equation. Results showed that tomatoes stored in the presence of light exhibited an increased respiration rate and a faster preclimacteric phase. Lycopene content, total soluble solids, and maturity index increased in the presence of light. Hence, light increased the postharvest ripening of tomatoes, affecting their shelf life.
Recently, bismuth oxyiodide (BiOI) is an attractive semiconductor to use in heterogeneous photoca... more Recently, bismuth oxyiodide (BiOI) is an attractive semiconductor to use in heterogeneous photocatalysis processes. Unfortunately, BiOI individually shows limited photocatalytic efficiency, instability, and a quick recombination of electron/holes. Considering the practical application of this semiconductor, some studies show that synthetic zeolites provide good support for this photocatalyst. This support material permits a better photocatalytic efficiency because it prevents the quick recombination of photogenerated pairs. However, the optimal conditions (time and temperature) to obtain composites (BiOI/ synthetic zeolite) with high photocatalytic efficiency using a coprecipitation-solvothermal growth method have not yet been reported. In this study, a response surface methodology (RSM) based on a central composite design (CCD) was applied to optimize the synthesis conditions of BiOI/mordenite composites. For this purpose, eleven BiOI/mordenite composites were synthesized using a c...
Benzothiazoles are organic compounds that may produce negative environmental impact when released... more Benzothiazoles are organic compounds that may produce negative environmental impact when released into watercourses. In particular, 2- mercaptobenzothiazole (MBT) are known to be toxic and hard to biodegrade. Activated carbon adsorption and ozonation have been identified as suitable treatment for those contaminants. However, there is some controversy about the effect of carbon surface chemical composition on the MBT adsorption. This paper focuses on this issue and presents experimental adsorption isotherms for MBT on Filtrasorb-400 activated carbon treated with different ozone doses. The activated carbon surface chemical properties were assessed by acid/basic neutralization, temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and the point of zero charge (pHPZC). Results show that ozone treatment modified the oxygenated groups on the activated carbon surface, increasing the concentration of acid groups, and reducing the pHPZC. Finally, ozone treatment le...
Journal of Environmental Chemical Engineering, 2021
Abstract Low frequency (40 kHz) ultrasound-assisted technique was utilized in the synthesis of Co... more Abstract Low frequency (40 kHz) ultrasound-assisted technique was utilized in the synthesis of CoFe2O4, GaOOH and α-Ga2O3 nanorods. CoFe2O4 was tethered successfully at the crystal matrices of GaOOH and α-Ga2O3 nanorods to form heterojunction nanocatalysts (CoFe2O4/GaOOH; CoFe2O4/Ga2O3). The heterojunction nanocatalysts were characterized using various analytical tools to confirm the expected modifications. The band gap of GaOOH (Eg = 4.50 eV) and α-Ga2O3 (Eg = 4.46 eV) are reduced in the formed heterojunction nanocatalysts CoFe2O4/GaOOH (Eg =2.56 eV) and CoFe2O4/Ga2O3 (Eg = 2.51 eV), respectively. Moreover, the XRD and HR-TEM analyses demonstrate the formation of heterojunction nanocatalysts composed of the lattice diffusion of Co and Fe of CoFe2O4 into the matrix of α-Ga2O3 nanorods with good crystallinity. The photocatalytic efficiency was assessed during solar light-driven photocatalyic oxidation of norflurazon in single treatments and also assisted by peroxymonosulfate addition. The experimental results indicate that ~ 98% of the norflurazon (NRF) is oxidized within 40 min of solar light irradiation in the presence of CoFe2O4/α-Ga2O3 heterojunction nanophotocatalyst, having higher photocatalytic efficiency than benchmarked TiO2 nanoparticles (Degussa P25). Moreover, the results also show that the addition of peroxymonosulfate (PMS) boosts the photocatalytic oxidation and achieving 99% NRF oxidation within 10 min of solar light irradiation by the generation of SO4•− and •OH radicals. The novel synthesized heterojunction nanophotocatalyst (CoFe2O4/α-Ga2O3) results to be highly stable after six consecutive operating cycles.
Benzothiazoles are emerging chemical pollutants mainly coming from leather, paper and rubber indu... more Benzothiazoles are emerging chemical pollutants mainly coming from leather, paper and rubber industries; due to their use as: herbicides, corrosion inhibitors, anti-freezers, and vulcanisation accelerators. This article presents experimental data on ozone treatment of benzothiazole contaminated waters. The effect of the initial concentration of benzothiazole, ozone dosage, temperature (10-30 °C), and pH (2-9), on ozonation removal rate were assessed at bench scale. Experimental results show that reaction between ozone and benzothiazole could be approximated to a second-order kinetic law. Kinetic parameters for direct and indirect ozone reactions are estimated and temperature dependence of rate parameters is evaluated. Moreover, an initial degradation pathway of benzothiazole ozonation is proposed.
In wastewater treatment facilities, air quality is not only affected by conventional unpleasant o... more In wastewater treatment facilities, air quality is not only affected by conventional unpleasant odour compounds; toxic volatile organic compounds (VOCs) are also found. In this study, the adsorptive capacity of Chilean natural zeolite toward VOC removal was evaluated. Moreover, the influence of zeolite chemical surface properties on VOC elimination was also investigated. Three modified zeolite samples were prepared from a natural Chilean zeolite (53% clinoptilolite, 40% mordenite and 7% quartz). Natural and modified zeolite samples were characterised by nitrogen adsorption at 77 K, elemental analyses and X-ray fluorescence (XRF). Chemical modifications of natural zeolite showed the important role of Brønsted acid sites on the abatement of VOCs. The presence of humidity has a negative effect on zeolite adsorption capacity. Natural zeolites could be an interesting option for benzene, toluene and xylene vapour emission abatement.
Journal of Environmental Chemical Engineering, 2021
Abstract Monodispersed silver quantum dots (Ag QDs) of sub 5 nm range are prepared through a faci... more Abstract Monodispersed silver quantum dots (Ag QDs) of sub 5 nm range are prepared through a facile and size-controllable green synthesis route using sweet lime (Citrus limetta) peel (SLP) extract. Powder X-ray diffraction studies confirm the formation of face-centered-cubic structured Ag QDs which is corroborated by selected area electron diffraction. The Ag QDs show an absorption maximum at ~415 nm due to characteristic surface plasmon resonance. The Ag QDs prepared at 80 °C exhibit high photoluminescence quenching, indicating low recombination rate and high lifetime of photoexcited electrons. The examination of SLP extract by Fourier-transform infrared spectroscopy, LC-MS and NMR spectroscopy reveals the presence of citrate and carbohydrate biomolecules that could be responsible for the formation of small and stable Ag QDs. The cytotoxic studies indicate that the synthesized Ag QDs are able to effect 71% cancer cells death at 100 µg/mL concentration. Moreover, Ag QDs exhibit minimum inhibitory concentration (MIC) value of 50 μg/mL against all the selected pathogenic bacteria. Present findings suggest that Ag QDs obtained by SLP extract mediated green synthesis can be employed as a low-cost and eco-friendly biocidal agent.
Abstract This study describes theoretical and experimental considerations to optimize the photoca... more Abstract This study describes theoretical and experimental considerations to optimize the photocatalytic degradation of caffeic acid in water using 3D-BiOBr based materials under visible light irradiation. Three BiOBr materials were synthesized through the solvothermal method using different bromide sources, namely potassium bromide (KBr) and the ionic liquid (IL) 1-butyl-3-methylimidazolium bromide. Morphological and chemical changes were observed in IL based 3D-BiOBr materials. The theoretical optimization of the experimental conditions in heterogeneous photocatalysis tests (pH and dose of catalyst) were simulated using the MODDE 12.0.1 software. A central composite design (CCD) was applied to obtain a response surface to elucidate the optimal conditions. This model predicted that the maximum photocatalytic degradation can be achieved at pH of 6.7 and a photocatalyst dose of 344 mg L−1. The optimal experimental conditions were tested using the three synthesized 3D-BiOBr materials. The results showed that the highest degradation efficiency and mineralization yield were obtained using the BiOBr microspheres synthesized with the IL at 145 °C.
Benzothiazole (BT) is a toxic and poorly biodegradable contaminant, usually found in wastewater f... more Benzothiazole (BT) is a toxic and poorly biodegradable contaminant, usually found in wastewater from rubber related applications. This compound could be effectively eliminated using advanced treatment processes. This paper compares experimental results on detoxification systems based on ozone oxidation, activated carbon adsorption, and simultaneous adsorption-oxidation using ozone in the presence of activated carbon. The effect of pH (2–11), and the presence of radical scavengers (tert-butyl alcohol and sodium carbonate) on process rates and removal efficiencies are assessed at laboratory scale. The experimental system consisted of a 1L differential circular flow reactor and an ozone generator rated at 5g O3/h. Results show that ozone oxidation combined with activated carbon adsorption increases the overall BT oxidation rate with respect to the ozonation process and activated carbon adsorption. In the presence of free radical scavenger, only a 44% reduction in BT removal rate is obs...
This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the p... more This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the presence of activated carbon, with a view to assessing possible changes in its surface chemical structure and adsorption capacity. Experiments were conducted in a 0.5 L reactor, loaded with 2 g Filtrasorb 400 granular activated carbon, and 1-5 mM DHB aqueous solution at pH 2-8. Ozone gas was generated with an Ozocav generator, and fed into the reactor for a given exposure time, in the range 0.5-240 min, at 25°C and 1 atm. After each run, liquid and activated carbon samples were taken for chemical assays. Soluble organic groups present on the active carbon surface were desorbed and analysed by GC-MS and HPLC. Activated carbon chemical surface properties were analysed using TPD, FT-IR, and XPS techniques. Reactions between ozone and adsorbed DHB were shown to be fast, leading to formation of C-6, C-4 and C-2 by-products. Oxygenated surface groups, particularly, COOH and C = O, increased as ...
This work aims to present experimental results on the treatment of methylene blue contaminated wa... more This work aims to present experimental results on the treatment of methylene blue contaminated waters using heterogeneous catalytic ozonation promoted by volcanic sand. The effect of pH (2–8), and the presence of radical scavengers (acetate ions) in homogeneous and heterogeneous systems are evaluated at laboratory scale. Heterogeneous catalytic ozonation using volcanic sand increases methylene blue removal rate. In the presence of free radical scavengers, only a 37% reduction on methylene blue removal rate is observed in the heterogeneous system, as compared with 70% when homogeneous ozonation is used. The results obtained here indicate the importance of chemical surface properties on methylene blue oxidation reactions, suggesting that acid surface sites of volcanic sand play a key role on the reaction mechanism.
In this article, the role of surface sites of modified zeolites with semiconductor nanoparticles ... more In this article, the role of surface sites of modified zeolites with semiconductor nanoparticles as alternative photocatalyts for protecting post-harvest foodstuff from the detrimental effects of ethylene is addressed. Two single and one double catalyst based on zinc and copper oxides supported over modified zeolite samples were prepared. Physical, chemical, and surface properties of prepared materials were studied by several characterization methods. UV-Vis absorption spectra show that the applied modification procedures increase the optical absorption of light in the UV and visible regions, suggesting that an increase in the photocatalytic activity could take place mainly in the obtained co-impregnated catalyst. An ethylene conversion around 50% was achieved when the parent natural zeolite support was modified with both transition metal oxides, obtaining higher removal efficiency in comparison to single oxide catalysts. Adsorption and photocatalytic oxidation experiments were also...
Tomatoes (Solanum lycopersicum L.) are widely cultivated and consumed, but ripening should be car... more Tomatoes (Solanum lycopersicum L.) are widely cultivated and consumed, but ripening should be carried out in controlled storage conditions to extend their shelf life and avoid economic losses. The aim of this study was to investigate the effects of visible artificial light on the ripening and quality of fresh market tomatoes stored at a low temperature and high humidity. The postharvest performance with respect to the ripening of organically grown tomatoes in the Toscano cultivar, with a long storage life, was studied in the presence and the absence of visible LED light. The maturation kinetics of the tomatoes was modeled using the Power Law equation. Results showed that tomatoes stored in the presence of light exhibited an increased respiration rate and a faster preclimacteric phase. Lycopene content, total soluble solids, and maturity index increased in the presence of light. Hence, light increased the postharvest ripening of tomatoes, affecting their shelf life.
Recently, bismuth oxyiodide (BiOI) is an attractive semiconductor to use in heterogeneous photoca... more Recently, bismuth oxyiodide (BiOI) is an attractive semiconductor to use in heterogeneous photocatalysis processes. Unfortunately, BiOI individually shows limited photocatalytic efficiency, instability, and a quick recombination of electron/holes. Considering the practical application of this semiconductor, some studies show that synthetic zeolites provide good support for this photocatalyst. This support material permits a better photocatalytic efficiency because it prevents the quick recombination of photogenerated pairs. However, the optimal conditions (time and temperature) to obtain composites (BiOI/ synthetic zeolite) with high photocatalytic efficiency using a coprecipitation-solvothermal growth method have not yet been reported. In this study, a response surface methodology (RSM) based on a central composite design (CCD) was applied to optimize the synthesis conditions of BiOI/mordenite composites. For this purpose, eleven BiOI/mordenite composites were synthesized using a c...
Benzothiazoles are organic compounds that may produce negative environmental impact when released... more Benzothiazoles are organic compounds that may produce negative environmental impact when released into watercourses. In particular, 2- mercaptobenzothiazole (MBT) are known to be toxic and hard to biodegrade. Activated carbon adsorption and ozonation have been identified as suitable treatment for those contaminants. However, there is some controversy about the effect of carbon surface chemical composition on the MBT adsorption. This paper focuses on this issue and presents experimental adsorption isotherms for MBT on Filtrasorb-400 activated carbon treated with different ozone doses. The activated carbon surface chemical properties were assessed by acid/basic neutralization, temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and the point of zero charge (pHPZC). Results show that ozone treatment modified the oxygenated groups on the activated carbon surface, increasing the concentration of acid groups, and reducing the pHPZC. Finally, ozone treatment le...
Journal of Environmental Chemical Engineering, 2021
Abstract Low frequency (40 kHz) ultrasound-assisted technique was utilized in the synthesis of Co... more Abstract Low frequency (40 kHz) ultrasound-assisted technique was utilized in the synthesis of CoFe2O4, GaOOH and α-Ga2O3 nanorods. CoFe2O4 was tethered successfully at the crystal matrices of GaOOH and α-Ga2O3 nanorods to form heterojunction nanocatalysts (CoFe2O4/GaOOH; CoFe2O4/Ga2O3). The heterojunction nanocatalysts were characterized using various analytical tools to confirm the expected modifications. The band gap of GaOOH (Eg = 4.50 eV) and α-Ga2O3 (Eg = 4.46 eV) are reduced in the formed heterojunction nanocatalysts CoFe2O4/GaOOH (Eg =2.56 eV) and CoFe2O4/Ga2O3 (Eg = 2.51 eV), respectively. Moreover, the XRD and HR-TEM analyses demonstrate the formation of heterojunction nanocatalysts composed of the lattice diffusion of Co and Fe of CoFe2O4 into the matrix of α-Ga2O3 nanorods with good crystallinity. The photocatalytic efficiency was assessed during solar light-driven photocatalyic oxidation of norflurazon in single treatments and also assisted by peroxymonosulfate addition. The experimental results indicate that ~ 98% of the norflurazon (NRF) is oxidized within 40 min of solar light irradiation in the presence of CoFe2O4/α-Ga2O3 heterojunction nanophotocatalyst, having higher photocatalytic efficiency than benchmarked TiO2 nanoparticles (Degussa P25). Moreover, the results also show that the addition of peroxymonosulfate (PMS) boosts the photocatalytic oxidation and achieving 99% NRF oxidation within 10 min of solar light irradiation by the generation of SO4•− and •OH radicals. The novel synthesized heterojunction nanophotocatalyst (CoFe2O4/α-Ga2O3) results to be highly stable after six consecutive operating cycles.
Benzothiazoles are emerging chemical pollutants mainly coming from leather, paper and rubber indu... more Benzothiazoles are emerging chemical pollutants mainly coming from leather, paper and rubber industries; due to their use as: herbicides, corrosion inhibitors, anti-freezers, and vulcanisation accelerators. This article presents experimental data on ozone treatment of benzothiazole contaminated waters. The effect of the initial concentration of benzothiazole, ozone dosage, temperature (10-30 °C), and pH (2-9), on ozonation removal rate were assessed at bench scale. Experimental results show that reaction between ozone and benzothiazole could be approximated to a second-order kinetic law. Kinetic parameters for direct and indirect ozone reactions are estimated and temperature dependence of rate parameters is evaluated. Moreover, an initial degradation pathway of benzothiazole ozonation is proposed.
In wastewater treatment facilities, air quality is not only affected by conventional unpleasant o... more In wastewater treatment facilities, air quality is not only affected by conventional unpleasant odour compounds; toxic volatile organic compounds (VOCs) are also found. In this study, the adsorptive capacity of Chilean natural zeolite toward VOC removal was evaluated. Moreover, the influence of zeolite chemical surface properties on VOC elimination was also investigated. Three modified zeolite samples were prepared from a natural Chilean zeolite (53% clinoptilolite, 40% mordenite and 7% quartz). Natural and modified zeolite samples were characterised by nitrogen adsorption at 77 K, elemental analyses and X-ray fluorescence (XRF). Chemical modifications of natural zeolite showed the important role of Brønsted acid sites on the abatement of VOCs. The presence of humidity has a negative effect on zeolite adsorption capacity. Natural zeolites could be an interesting option for benzene, toluene and xylene vapour emission abatement.
Journal of Environmental Chemical Engineering, 2021
Abstract Monodispersed silver quantum dots (Ag QDs) of sub 5 nm range are prepared through a faci... more Abstract Monodispersed silver quantum dots (Ag QDs) of sub 5 nm range are prepared through a facile and size-controllable green synthesis route using sweet lime (Citrus limetta) peel (SLP) extract. Powder X-ray diffraction studies confirm the formation of face-centered-cubic structured Ag QDs which is corroborated by selected area electron diffraction. The Ag QDs show an absorption maximum at ~415 nm due to characteristic surface plasmon resonance. The Ag QDs prepared at 80 °C exhibit high photoluminescence quenching, indicating low recombination rate and high lifetime of photoexcited electrons. The examination of SLP extract by Fourier-transform infrared spectroscopy, LC-MS and NMR spectroscopy reveals the presence of citrate and carbohydrate biomolecules that could be responsible for the formation of small and stable Ag QDs. The cytotoxic studies indicate that the synthesized Ag QDs are able to effect 71% cancer cells death at 100 µg/mL concentration. Moreover, Ag QDs exhibit minimum inhibitory concentration (MIC) value of 50 μg/mL against all the selected pathogenic bacteria. Present findings suggest that Ag QDs obtained by SLP extract mediated green synthesis can be employed as a low-cost and eco-friendly biocidal agent.
Abstract This study describes theoretical and experimental considerations to optimize the photoca... more Abstract This study describes theoretical and experimental considerations to optimize the photocatalytic degradation of caffeic acid in water using 3D-BiOBr based materials under visible light irradiation. Three BiOBr materials were synthesized through the solvothermal method using different bromide sources, namely potassium bromide (KBr) and the ionic liquid (IL) 1-butyl-3-methylimidazolium bromide. Morphological and chemical changes were observed in IL based 3D-BiOBr materials. The theoretical optimization of the experimental conditions in heterogeneous photocatalysis tests (pH and dose of catalyst) were simulated using the MODDE 12.0.1 software. A central composite design (CCD) was applied to obtain a response surface to elucidate the optimal conditions. This model predicted that the maximum photocatalytic degradation can be achieved at pH of 6.7 and a photocatalyst dose of 344 mg L−1. The optimal experimental conditions were tested using the three synthesized 3D-BiOBr materials. The results showed that the highest degradation efficiency and mineralization yield were obtained using the BiOBr microspheres synthesized with the IL at 145 °C.
Benzothiazole (BT) is a toxic and poorly biodegradable contaminant, usually found in wastewater f... more Benzothiazole (BT) is a toxic and poorly biodegradable contaminant, usually found in wastewater from rubber related applications. This compound could be effectively eliminated using advanced treatment processes. This paper compares experimental results on detoxification systems based on ozone oxidation, activated carbon adsorption, and simultaneous adsorption-oxidation using ozone in the presence of activated carbon. The effect of pH (2–11), and the presence of radical scavengers (tert-butyl alcohol and sodium carbonate) on process rates and removal efficiencies are assessed at laboratory scale. The experimental system consisted of a 1L differential circular flow reactor and an ozone generator rated at 5g O3/h. Results show that ozone oxidation combined with activated carbon adsorption increases the overall BT oxidation rate with respect to the ozonation process and activated carbon adsorption. In the presence of free radical scavenger, only a 44% reduction in BT removal rate is obs...
This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the p... more This work aims at obtaining experimental data on ozonation of 1,2-dihydroxybenzene (DHB) in the presence of activated carbon, with a view to assessing possible changes in its surface chemical structure and adsorption capacity. Experiments were conducted in a 0.5 L reactor, loaded with 2 g Filtrasorb 400 granular activated carbon, and 1-5 mM DHB aqueous solution at pH 2-8. Ozone gas was generated with an Ozocav generator, and fed into the reactor for a given exposure time, in the range 0.5-240 min, at 25°C and 1 atm. After each run, liquid and activated carbon samples were taken for chemical assays. Soluble organic groups present on the active carbon surface were desorbed and analysed by GC-MS and HPLC. Activated carbon chemical surface properties were analysed using TPD, FT-IR, and XPS techniques. Reactions between ozone and adsorbed DHB were shown to be fast, leading to formation of C-6, C-4 and C-2 by-products. Oxygenated surface groups, particularly, COOH and C = O, increased as ...
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