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This work focuses on the comparison of the performance of direct electrochemical oxidation with indirect electrolysis mediated by gaseous oxidants in the treatment of diluted wastewater. To do this, energy consumptions of the electrolysis using mixed metal oxide (MMO) electrodes are compared with those required for the production and use of chlorine dioxide in the degradation of methomyl contained in aqueous solutions. Results demonstrate the feasibility of the mediated oxidation process and that this process is competitive with direct oxidation. The oxidants are produced under optimized conditions using the same anodic material applied for the direct degradation of organics, thus avoiding efficiency losses associated with mass transfer limitations in the degradation of dilute organic solutions. Thus, using the ClO2 gaseous oxidant, a concentration of 0.1 mM of methomyl from a solution containing 500 mL is completely removed with an energy consumption as low as 50 Wh. The application of the same energy to a direct electrolytic process for treating the same wastewater can only reach less than half of this removal. These findings may have a very important application in the use of electrochemical technology to achieve the remediation of persistent pollutants in wastewater, where their low concentrations typically make direct processes very inefficient.

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Hydrogen peroxide (H2O2) stands as one of the foremost utilized oxidizing agents in modern times. The established method for its production involves the intricate and costly anthraquinone process. However, a promising alternative pathway is the electrochemical hydrogen peroxide production, accomplished through the oxygen reduction reaction via a 2-electron pathway. This method not only simplifies the production process but also upholds environmental sustainability, especially when compared to the conventional anthraquinone method. In this review paper, recent works from the literature focusing on the 2-electron oxygen reduction reaction promoted by carbon electrocatalysts are summarized. The practical applications of these materials in the treatment of effluents contaminated with different pollutants (drugs, dyes, pesticides, and herbicides) are presented. Water treatment aiming to address these issues can be achieved through advanced oxidation electrochemical processes such as electro-Fenton, solar-electro-Fenton, and photo-electro-Fenton. These processes are discussed in detail in this work and the possible radicals that degrade the pollutants in each case are highlighted. The review broadens its scope to encompass contemporary computational simulations focused on the 2-electron oxygen reduction reaction, employing different models to describe carbon-based electrocatalysts. Finally, perspectives and future challenges in the area of carbon-based electrocatalysts for H2O2 electrogeneration are discussed. This review paper presents a forward-oriented viewpoint of present innovations and pragmatic implementations, delineating forthcoming challenges and prospects of this ever-evolving field.

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Recent studies reported a new strategy of electro-oxidation of organic compounds using methanol as solvent. Considering its well-known toxicity, this work sought to evaluate the use of ethanol as an alternative solvent for pollutants degradation. Therefore, thorough analyses were performed in order to evaluate tetracycline (TC) electro-oxidation using DSA-Cl2 anode in ethanol-H2O solutions. The effects of solvent mixture, pH and current density on the degradation efficiency were evaluated. TC degradation in methanol-water and ethanol-water media resulted in very close removals of 95% and 90%, respectively, after 15 min of electrolysis at 10 mA cm-2. In ethanol medium, the increase in current densities from 10 to 25 mA cm-2 did not lead to significant changes in removal efficiency. The variation of the initial pH of the solution showed that the best removal efficiencies were obtained at neutral pH resulting in TC removals up to 90%, which is actually related to the molecular structure of TC. Through analysis using electron paramagnetic resonance (EPR), the formation of radicals such as hydroxyethyl (CH3●CHOH), hydroxyl (●OH) and ethoxy (CH3CH2O●) were detected, which effectively contributed toward the pollutant oxidation.

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This work reports the radicals detected and identified during the degradation of atrazine in methanol medium in the presence and absence of different proportions of water (0%, 5%, and 10%). The determination of these radicals is an important step to understand the electrolysis processes in methanol medium and contribute to clarify the degradation mechanism. Furthermore, the parameters for the successful removal of the contaminant were optimized and the results showed that the application of the technique led to the removal of nearly 99.8% of atrazine after 1 h of electrolysis. The oxidation kinetics was found to be very fast and most of the atrazine molecule in the medium was degraded in the first hour of electrolysis. The results obtained from a thorough analysis conducted with a view to evaluating the effects of different current densities and initial pH values on atrazine degradation showed that the application of higher current densities resulted in lower energy consumption, as this led to faster removal of atrazine. Additionally, the initial pH of the solution was found to favor the formation of different species of active chlorine. The radicals formed during the electro-oxidation process were detected by electron paramagnetic resonance spectroscopy and include hydroxyl, methoxy and hydroxymethyl. The use of methanol for the degradation of pollutants is a highly promising technique and this work shows that the identification of the different radicals formed in the process can be the key to understanding the degradation mechanism.

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The electro-oxidation of tetracycline (TeC) in methanol medium containing chloride or sulfate ions was evaluated using a DSA®-Cl2 in a flow reactor and compared with BDD. The results show that after 30 min of electrolysis no TeC is detected by liquid chromatography when chloride is used as supporting electrolyte. On the other hand, after 90 min of electrolysis using a BDD anode only 61% of TeC was removed from solutions with chloride, but in the presence of sulfate the removal reaches 94%. This evidences that the oxidizing species generated during electrochemical oxidation control the process and the mechanism of degradation of the TeC. Besides that, it was possible to infer that only a small amount of methanol might convert to formaldehyde or formic acid, although they were not detected according to the nil changes in the FTIR spectra or in the HPLC chromatograms recorded.

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The objective of this work was a systemic evaluation of the anodizing treatment in a ß-type Ti-15Mo alloy to grow a TiO2 nanostructured layer for osseointegration improvement. The technical viability of the surface modification was assessed based on the resistance to mechanical fatigue, electrochemical corrosion, and biological response. By using an organic solution of NH4 F in ethylene glycol, a well-organized array of 90 nm diameter nanotubes was obtained with a potential of 40 V for 6 h, while undefined nanotubes of 25 nm diameter were formed with a potential of 20 V for 1 h. Nevertheless, the production of the 90 nm diameter nanotubes was followed by micrometer pits that significantly reduced the fatigue performance. The undefined nanotubes of 25 nm diameter, besides the greater cell viability and improved osteoblastic cell differentiation in comparison to the as-polished surface, were not deleterious to the fatigue and corrosion properties. This result strengthens the necessity of an overall evaluation of the anodizing treatment, particularly the fatigue resistance, before suggesting it for the design of implants. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 86-96, 2019.

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This study investigated the anodic oxidation of phenolic wastewater generated by cashew-nut processing industry (CNPI) using active (Ti/RuO2-TiO2) and inactive (boron doped diamond, BDD) anodes. During electrochemical treatment, various operating parameters were investigated, such as current density, chemical oxygen demand (COD), total phenols, O2 production, temperature, pH, as well as current efficiency and energy consumption. After electrolysis under optimized working conditions, samples were evaluated by chromatography and toxicological tests against L. sativa. When both electrode materials were compared under the same operating conditions, higher COD removal efficiency was achieved for BDD anode; achieving lower energy requirements when compared with the values estimated for Ti/RuO2-TiO2. The presence of Cl- in the wastewater promoted the electrogeneration of strong oxidant species as chlorine, hypochlorite and mainly hypochlorous acid, increasing the efficiency of degradation process. Regarding the temperature effect, BDD showed slower performances than those achieved for Ti/RuO2-TiO2. Chromatographic and phytotoxicity studies indicated formation of some by-products after electrolytic process, regardless of the anode evaluated, and phytotoxic action of the effluent. Results encourage the applicability of the electrochemical method as wastewater treatment process for the CNPI, reducing depuration time.

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The photo-assisted electrochemical degradation of a real effluent of the atrazine manufacturing process containing atrazine, simazine, hydroxy-triazine and propazine was carried out galvanostatically using a pilot-scale tubular flow reactor prototype containing DSA® and Ti as cathode. The effluent was mainly characterized by a high amount of NaCl, required in the synthesis route used, and it was used as taken in the factory. The variables for process optimization were the current density (3.0, 6.0, and 9.0 mA cm-2) and flow rate (300 and 3,000 L h-1). These later values produces laminar and turbulent flow regimes, with Reynolds numbers of 1,100 and 11,000, respectively. None of the four organics contained in the waste is refractory to the photo-electrochemical treatment and they are depleted with the photo-electrolytic technology using large current densities and appropriate electric charge passed. Both direct electrochemical process and mediated anodic oxidation occur during the treatment. First process occurs at turbulent flow condition and low current densities, while the chemical oxidation process happens at laminar flow condition and high current densities. Atrazine and propazine are efficiently removed at laminar flow conditions, with an almost total depletion for the largest current densities. On the contrary, simazine is efficiently removed in turbulent flow conditions and intermediate current density, with removals higher than 90% for 20 kWh m-3. These results have great significance because they demonstrate the applicability of the electrochemical technology in the treatment of real industrial wastes with a cell specially designed to attain high efficiency in the removal of pollutants.

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The yeast Saccharomyces cerevisiae, a microorganism with cell walls resistant to many types of treatments, was chosen as a model to study electrochemical disinfection process using dimensionally stable anodes (DSA). DSA electrodes with nominal composition of Ti/RuO2TiO2 and Ti/RuO2TiO2IrO2 were evaluated in 0.05 mol L-1 Na2SO4 containing yeast. The results showed inactivation about of 100 % of the microorganisms at Ti/RuO2TiO2 by applying 20 and 60 mA cm-2 after 120 min of electrolysis, while a complete inactivation at Ti/RuO2IrO2TiO2 electrode was achieved after 180 min at 60 mA cm-2. When chloride ions were added in the electrolyte solution, 100 % of the yeast was inactivated at 20 mA cm-2 after 120 min of electrolysis, independent of the anode used. In the absence of chloride, the energy consumption (EC) was of 34.80 kWh m-3, at 20 mA cm-2 by using Ti/RuO2TiO2 anode. Meanwhile, in the presence of chloride, EC was reduced, requiring 30.24 and 30.99 kWh m-3 at 20 mA cm-2, for Ti/RuO2TiO2 and Ti/RuO2IrO2TiO2 electrodes, respectively, The best performance for cell lysis was obtained in the presence of chloride with EC of 88.80 kWh m-3 (Ti/RuO2TiO2) and 91.85 kWh m-3 (Ti/RuO2IrO2TiO2) to remove, respectively, 92 and 95 % of density yeast. The results clearly showed that yeast, as a model adopted, was efficiently inactivated and lysed by electrolysis disinfection using DSA-type electrodes.

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A comparative study was carried out of sonochemical (SCh), electrochemical (ECh) and sonoelectrochemical (SECh) strategies for the degradation of the fungicide thiram in dilute aqueous solution. The SCh and SECh studies were performed using a sonicator equipped with an 11 mm titanium-alloy probe and operated at 20 kHz with a power intensity of 523 W cm(-2). In the ECh and SECh investigations, galvanostatic electrolyses were implemented using a single compartment electrochemical cell with a boron-doped diamond electrode as anode and applied current densities in the range 10-50 mA cm(-2). For these processes, the decrease in concentration of thiram was monitored by high performance liquid chromatographic (HPLC) analysis and values of current efficiency and energy consumption were determined. The results showed that the rate of degradation of thiram and the amount of energy consumed were directly proportional to the applied current density, while current efficiency was inversely related to current density. The kinetics of thiram degradation followed a pseudo first order model with apparent rate constants in the region of 10(-3)min(-1). Thiram in aqueous solution was subjected to "exhaustive" degradation by ECh and SECh processes for 5h at applied current densities of 35 mA cm(-2) and the intermediates/byproducts so-formed were identified by HPLC-mass spectrometry. Mechanisms of the degradation reactions have been proposed on the basis of the results obtained.