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.

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.

Assessing the oxygen reduction reaction by a 2-electron mechanism on ceria surfaces.

The 2-electron pathway of the oxygen reduction reaction is an unwanted process in the development of fuel cells. In contrast, it has gained the scientific community's attention due to its importance as a promising way of removing emergent pollutants and endocrine disruptors from water bodies and a more sustainable alternative for large-scale commercial hydrogen peroxide production. Cerium oxide has shown remarkable potential and selectivity experimentally for this mechanism, and its possible applications, exceeding the previous reference materials. In this work, we studied the 2-electron pathway for oxygen reduction on different ceria-cleaving directions (100), (110), (221), and (331) by first principles methods based on density functional theory. Our results show that the (100) surface is the most favorable for reduction, with the (331) crystallographic plane also showing potential for good catalytic activity. This fact could be essential for designing new nanostructures, with higher portions of those planes exposed, for higher catalytic activity.

Removal of Orange II (OII) dye by simulated solar photoelectro-Fenton and stability of WO2.72/Vulcan XC72 gas diffusion electrode.

The objectives of this study were to determine the viability of removing Orange II (OII) dye by simulated solar photoelectro-Fenton (SSPEF) and to evaluate the stability of a WO2.72/Vulcan XC72 gas diffusion electrode (GDE) and thus determine its best operating parameters. The GDE cathode was combined with a BDD anode for decolorization and mineralization of 350 mL of 0.26 mM OII by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF) at 100, 150 and 200 mA cm-2 and SSPEF at 150 mA cm-2. The GDE showed successful operation for electrogeneration, good reproducibility and low leaching of W. Decolorization and OII decay were directly proportional to the current density (j). AO-H2O2 had a reduced performance that was only half of the SSPEF, PEF and EF treatments. The mineralization efficiency was in the following order: AO-H2O2 < EF < PEF ≈ SSPEF. This showed that the GDE, BDD anode and light radiation combination was advantageous and indicated that the SSPEF process is promising with both a lower cost than using UV lamps and simulating solar photoelectro-Fenton process. The PEF process with the lowest j (100 mA cm-2) showed the best performance-mineralization current efficiency.

Electrochemical incineration of the antibiotic ciprofloxacin in sulfate medium and synthetic urine matrix.

The degradation of 100 mL of 0.245 mM of the antibiotic ciprofloxacin in 0.05 M Na2SO4 at pH 3.0 has been studied by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF). Electrolyses were performed with a stirred tank reactor using either a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode. In EF, PEF and SPEF, ciprofloxacin was rapidly removed due to its oxidation with (•)OH formed from Fenton's reaction between added Fe(2+) and H2O2 generated at the cathode. The larger electrochemical incineration of the antibiotic was achieved by SPEF with BDD with 95% mineralization thanks to the additional attack by hydroxyl radicals formed from water oxidation at the BDD anode surface and the photolysis of final Fe(III)-oxalate and Fe(III)-oxamate species from sunlight. Up to 10 primary intermediates and 11 hydroxylated derivatives were identified by LC-MS, allowing the proposal of a reaction sequence for ciprofloxacin mineralization. A different behavior was found when the same antibiotic concentration was oxidized in a synthetic urine matrix with high urea content and a mixture of PO4(3-), SO4(2-) and Cl(-) ions. Since Fenton's reaction was inhibited in this medium, only EO and EO-H2O2 processes were useful for mineralization, being the organics mainly degraded by HClO formed from Cl(-) oxidation. The EO process with a BDD/stainless steel cell was found to be the most powerful treatment for the urine solution, yielding 96% ciprofloxacin removal and 98% mineralization after 360 min of electrolysis at optimum values of pH 3.0 and current density of 66.6 mA cm(-2). The evolution of released inorganic ions was followed by ion chromatography.

DFT and electrochemical studies on nortriptyline oxidation sites.

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule's activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.

Electrochemical oxidation of benzene on boron-doped diamond electrodes.

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H2SO4 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1x10(-2) M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10(-5) M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.