Hydrogen peroxide electrogeneration from O2 electroreduction: A review focusing on carbon electrocatalysts and environmental applications.

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.

A review on recent environmental electrochemistry approaches for the consolidation of a circular economy model.

Availability of raw materials in the chemical industry is related to the selection of the chemical processes in which they are used as well as to the efficiency, cost, and eventual evolution to more competitive dynamics of transformation technologies. In general terms however, any chemically transforming technology starts with the extraction, purification, design, manufacture, use, and disposal of materials. It is important to create a new paradigm towards green chemistry, sustainability, and circular economy in the chemical sciences that help to better employ, reuse, and recycle the materials used in every aspect of modern life. Electrochemistry is a growing field of knowledge that can help with these issues to reduce solid waste and the impact of chemical processes on the environment. Several electrochemical studies in the last decades have benefited the recovery of important chemical compounds and elements through electrodeposition, electrowinning, electrocoagulation, electrodialysis, and other processes. The use of living organisms and microorganisms using an electrochemical perspective (known as bioelectrochemistry), is also calling attention to "mining", through plants and microorganisms, essential chemical elements. New process design or the optimization of the current technologies is a major necessity to enhance production and minimize the use of raw materials along with less generation of wastes and secondary by-products. In this context, this contribution aims to show an up-to-date scenario of both environmental electrochemical and bioelectrochemical processes for the extraction, use, recovery and recycling of materials in a circular economy model.

A review of electro-Fenton and ultrasound processes: towards a novel integrated technology for wastewater treatment.

Nowadays, the presence of persistent dissolved pollutants in water has received increasing attention due to their toxic effects on living organisms. Considering the limitations of conventional wastewater treatment processes for the degradation of these compounds, advanced oxidation processes such as electro-Fenton and sono-chemical process, as well as their combination, appear as potentially effective options for the treatment of wastewater contaminated with bio-recalcitrant pollutants. In view of the importance of the development of processes using real effluents, this review aims to provide a comprehensive perspective of sono-electro-Fenton-related processes applied for real wastewater treatment. In the first section, the fundamentals and effectiveness of both homogeneous and heterogeneous electro-Fenton approaches for the treatment of real wastewater are presented. While the second part of this work describes the fundamentals of ultrasound-based processes, the last section focuses on the coupling of the two methods for real wastewater treatment and on the effect of the main operational parameters of the process. On the basis of the information presented, it is suggested that sono-electro-Fenton processes substantially increase the efficiency of the treatment as well as the biodegradability of the treated wastewater. The combined effect results from mass transfer improvement, electrode cleaning and activation, water electrolysis, and the electro-Fenton-induced production of hydroxyl radicals. The information presented in this work is expected to be useful for closing the gap between laboratory-scale assays and the development of novel wastewater technologies.

Decontamination of wastewater containing contaminants of emerging concern by electrooxidation and Fenton-based processes - A review on the relevance of materials and methods.

In recent years, there has been an increasingly growing interest regarding the use of electrochemical advanced oxidation processes (EAOPs) which are considered highly promising alternative treatment techniques for addressing environmental issues related to pollutants of emerging concern. In EAOPs, electrogenerated oxidizing agents, such as hydroxyl radical (HO•), can react non-selectively with a wide range of organic compounds, degrading and mineralizing their structures to unharmful molecules like CO2, H2O, and inorganic ions. To this date, a broad spectrum of advanced electrocatalysts have been developed and applied for the treatment of compounds of interest in different matrices, specifically aiming at enhancing the degradation performance. New combined methods have also been employed as alternative treatment techniques targeted at circumventing the major obstacles encountered in Fenton-based processes, such as high costs and energy consumption, which still contribute significantly toward inhibiting the large-scale application of these processes. First, some fundamental aspects of EAOPs will be presented. Further, we will provide an overview of electrode materials which have been recently developed and reported in the literature, highlighting different anode and cathode structures employed in EAOPs, their main advantages and disadvantages, as well as their contribution to the performance of the treatment processes. The influence of operating parameters, such as initial concentrations, pH effect, temperature, supporting electrolyte, and radiation source, on the treatment processes were also studied. Finally, hybrid techniques which have been reported in the literature and critically assess the most recent techniques used for evaluating the degradation efficiency of the treatment processes.

Study of the performance of a cylindrical flow-through electro-Fenton reactor using different arrangements of carbon felt electrodes: effect of key operating parameters.

In this work, a cylindrical flow-through electro-Fenton reactor containing graphite felt electrodes and an Fe(II) loaded resin was evaluated for the production of the Fenton reaction mixture and for the degradation of amoxicillin (AMX) and fecal coliforms containing aqueous solutions. First, the influence of several factors such as treatment time, current intensity, flow rate, and electrode position was investigated for the electrogeneration of H2O2 and the energetic consumption by means of a factorial design methodology using a 24 factorial matrix. Electric current and treatment time were found to be the pivotal parameters influencing the H2O2 production with contributions of 40.2 and 26.9%, respectively. The flow rate had low influence on the responses; however, 500 mL min-1 (with an average residence time of 1.09 min obtained in the residence time distribution analysis) allowed to obtain a better performance due to the high mass transport to and from the electrodes. As expected, polarization was also found to play an important role, since for the cathode-to-anode flow direction, lower H2O2 concentrations were observed when compared with the anode-to-cathode flow arrangement, indicating that part of the H2O2 produced in the cathode was destroyed at the anode. A fluorescence study of hydroxyl radical production, on the other hand, showed that higher yields were obtained using an anode-to-cathode flow direction (up to 3.88 µM), when compared with experiments carried out using a cathode-to-anode flow path (3.11 µM). The removal of a commercial formulation of the antibiotic AMX was evaluated in terms of total organic carbon, achieving up to 57.9% and 38.63% of pollutant mineralization using synthetic and real sanitary wastewater spiked, respectively. Finally, the efficiency of the process on the inactivation of fecal coliforms in sanitary wastewater samples was assessed, reducing 90% of the bacteria after 5 min of electrolysis.

Experimental and Theoretical Insights on Methylene Blue Removal from Wastewater Using an Adsorbent Obtained from the Residues of the Orange Industry.

Chemical and thermochemical transformations were performed on orange peel to obtain materials that were characterized and further tested to explore their potential as adsorbents for the removal of methylene blue (MB) from aqueous solutions. The results show the high potential of some of these materials for MB adsorption not only due to the surface area of the resulting substrate but also to the chemistry of the corresponding surface functional groups. Fitting of the kinetic as well as the equilibrium experimental data to different models suggests that a variety of interactions are involved in MB adsorption. The overall capacities for these substrates (larger than 192.31 mg g-1) were found to compare well with those reported for activated carbon and other adsorbents of agro-industrial origin. According to these results and complementary with theoretical study using Density Functional Theory (DFT) approximations, it was found that the most important adsorption mechanisms of MB correspond to: (i) electrostatic interactions, (ii) H-bonding, and (iii) π (MB)-π (biochar) interactions. In view of these findings, it can be concluded that adsorbent materials obtained from orange peel, constitute a good alternative for the removal of MB dye from aqueous solutions.

Photo-assisted electrochemical advanced oxidation processes for the disinfection of aqueous solutions: A review.

Disinfection is usually the final step in water treatment and its effectiveness is of paramount importance in ensuring public health. Chlorination, ultraviolet (UV) irradiation and ozone (O3) are currently the most common methods for water disinfection; however, the generation of toxic by-products and the non-remnant effect of UV and O3 still constitute major drawbacks. Photo-assisted electrochemical advanced oxidation processes (EAOPs) on the other hand, appear as a potentially effective option for water disinfection. In these processes, the synergism between electrochemically produced active species and photo-generated radicals, improve their performance when compared with the corresponding separate processes and with other physical or chemical approaches. In photo-assisted EAOPs the inactivation of pathogens takes place by means of mechanisms that occur at different distances from the anode, that is: (i) directly at the electrode's surface (direct oxidation), (ii) at the anode's vicinity by means of electrochemically generated hydroxyl radical species (quasi-direct), (iii) or at the bulk solution (away from the electrode surface) by photo-electrogenerated active species (indirect oxidation). This review addresses state of the art reports concerning the inactivation of pathogens in water by means of photo-assisted EAOPs such as photo-electrocatalytic process, photo-assisted electrochemical oxidation, photo-electrocoagulation and cathodic processes. By focusing on the oxidation mechanism, it was found that while quasi-direct oxidation is the preponderant inactivation mechanism, the photo-electrocatalytic process using semiconductor materials is the most studied method as revealed by numerous reports in the literature. Advantages, disadvantages, trends and perspectives for water disinfection in photo-assisted EAOPs are also analyzed in this work.

Study of a coupled adsorption/electro-oxidation process as a tertiary treatment for tequila industry wastewater.

Vinasse wastewater from tequila industry that has been conventionally treated is usually characterized by a chemical oxygen demand (COD) above 150 mg L-1, which is the maximum content permitted for discharge by Mexican Regulation. In order to increase the wastewater quality, different processes were applied, and from the experimental results, the advantages and limitations were analyzed. In this way, although Fenton experiments showed acceptable COD removal efficiencies (79-90%), operation as well as cost limit its adoption as a viable technology. Therefore, additional experiments explored electro-Fenton (EF) as well as adsorption coupled to EF in a tubular reactor. The corresponding data revealed that there was no additional increase in COD removal performance probably due to the low oxygen solubility in the electrolytic solution and the high pH that prevents the existence of Fe2+ ions necessary for the Fenton mixture. In view of these results, when an activated carbon (AC) filter was coupled to polarization at current densities between 0.5 and 2 mA cm-2, removal efficiencies from 71 to 81%, corresponding to final COD of 78 to 33 mg L-1, were achieved. Also, the adsorbent surface was continuously regenerated, promoting a more efficient adsorption and a longer service life for the AC filter. In this case, by using a current density of 0.5 mA cm-2, COD was reduced to sufficiently small values for discharge into natural water bodies, maintaining low energy consumption and therefore acceptable operation costs.

Study of polarized activated carbon filters as simultaneous adsorbent and 3D-type electrode materials for electro-Fenton reactors.

Electro-Fenton (EF) based water treatment processes using activated carbon (AC) packed beds constitute an attractive approach for the development of competitive degradation technology of persistent pollutants in aqueous effluents. In this work, the results of a study aimed to assess the effect on the EF performance of different parameters of the reactor's operation are presented. By means of a factorial experimental design, the influence of the AC source (lignitic or vegetal), AC acid pre-treatment, particle size distribution and the amount of Fe loaded resin in the reactor were analyzed. From the resulting data it was found that the most influential parameter in the EF performance of the reactor is the AC source. Modest effects were observed for AC acid pre-treatment, which limits Fe ion adsorption on the AC substrate. The use of a wide particle distribution of AC particles was also found to improve inter-particle electrical contact, thus favoring the electrochemical processes that take place inside the reactor. An investigation on the effect of the amount of Fe in the reactor as well as its distribution dynamics, also revealed that an excess of Fe ions in the reactor decreases the EF performance of the system since Fe ions efficiently adsorb on the AC substrate, particularly in non- acid treated samples. The best operation conditions consisted on using un-meshed vegetable AC, without acid pretreatment in an EF reactor loaded with 0.25 g of Fe, which allowed to reach full color removal of bright blue FCP model dye in 70 min.

Inactivation of helminth eggs in an electro-Fenton reactor: Towards full electrochemical disinfection of human waste using activated carbon.

The disinfection of helminth eggs and Escherichia coli contaminated aqueous solutions, was studied using an electro-Fenton reactor equipped with a polarized activated carbon (AC) packed bed and two chambers loaded with cation exchange resins. Experiments using different arrangements and operation conditions, revealed that effective elimination of Escherichia coli takes place in all electrochemical disinfection tests. For the more resistant helminth eggs however, adsorption, electro-oxidation and electro-Fenton experiments showed retention within the reactor and pathogen inactivation values of 0, 16, and 25%, respectively. Using helminth eggs concentration data in different sections of the reactor, optical microscopy analysis and an exploratory computer simulation, differences in the disinfection performance were explained and new recirculation and flow direction and polarization switching operation schemes were defined. The corresponding experiments revealed that the effective coupling between adsorption and electro-Fenton phenomena, all along the AC packed bed compartment, results in 100% inactivation of helminth eggs.

Electrochemical degradation of triclosan in aqueous solution. A study of the performance of an electro-Fenton reactor.

The electro-Fenton degradation of Triclosan in aqueous solution was studied using a cylindrical reactor in which polarized carbon cloth electrodes and a cation exchange resin were employed. Using a factorial design of experiments approach, the effect of four variables (considering two levels for each one), was measured on four response parameters that reflect the electrooxidation efficiency of the electrochemical reactor. The results revealed that in all cases triclosan degradation was very efficient (above 95%) and that while there is a reasonable effect of all variables and their interactions, the one with the strongest influence on the process is the nature and magnitude of the ionic strength of the electrolytic solution. In this way, while the presence of a buffer species in this solution can keep the pH in a value that affects the generation of •OH radicals from the Fenton mixture, a high ionic strength solution can promote the elimination of Fe ionic species from the reactor by decreasing resin Fe retention due to competition effects of other ions for the binding sites of the substrate. HPLC experiments of the effluent solutions, also revealed that the degradation by-products of triclosan were dependent on the nature and ionic strength of the electrolytic solution in the electro-Fenton process under study. Finally, comparison of the different operation modes, also suggested that electro-adsorption of Fe cationic species in the negatively polarized cathode surface, is the main factor that controls Fe ion retention within the reactor.

Optimization of the integral valorization process for orange peel waste using a design of experiments approach: Production of high-quality pectin and activated carbon.

The aim of this study was to optimize the integral valorization of orange peel waste by obtaining activated carbon after a process of pectin recovery in recycling of orange peel by transformation to value-added products of pectin extraction and activated carbon preparation. The study was supported by statistical analysis, and the significant factors and optimal conditions were obtained from the statistical analysis. Using a representative sample of orange peel waste, a yield of 29.37% pectin was recovered at the optimal operating conditions (phosphoric acid as the extraction agent, 95 °C as the impregnation temperature and a 2-hour extraction time). Activated carbon (AC) was prepared from the remaining solid residue. The conditions that improve the resulting material quality were H3PO4 [0.6 M] used as the activating agent, an impregnation temperature of 95 °C, a carbonization temperature of 400 °C and 1 h of carbonization time. The obtained AC showed a sorption capacity of 2342.91 mg g-1, a value higher than that reported for commercial activated carbon. Using a model dye chemical, the sorption kinetics and thermodynamics of AC were found to follow a pseudo-second-order rate and the Freundlich models, respectively. Using the process conditions obtained in this study, it was possible to optimize the yield and also obtain good-quality products from valorization of orange peel.

Novel arrangement for an electro-Fenton reactor that does not require addition of iron, acid and a final neutralization stage. Towards the development of a cost-effective technology for the treatment of wastewater.

A novel arrangement for an electro-Fenton reactor aimed to treat neutral wastewater is presented. The arrangement consists on three-compartments in series, two of them packed with a cation exchange resin and one positioned between these, containing a polarized activated carbon column where the electrochemical generation of the Fenton reagent takes place. While the hydroxyl radicals electrochemically produced in-situ, react with the pollutant species adsorbed on the activated carbon cathode, the resin compartments administrate and collect the iron cation and the hydrated proton species in alternating flow direction cycles. The resulting process is a system that does not require acid or iron chemical addition to the process while at the same time, renders decontaminated water free of iron-dissolved species at neutral pH. The proposed electrochemical reactor arrangement is therefore the basis for the design of commercially viable electro-Fenton reactors in which the addition and subsequent removal of acid and iron chemicals is avoided; two of the currently most limiting features for the development of electro-Fenton technology for treating wastewater.