Electrochemical oxidation of 3-methylpyridine at a boron-doped diamond electrode: application to electroorganic synthesis and wastewater treatment

The electrochemical oxidation of 3-methylpyridine (3-MP) at synthetic boron-doped diamond (BDD) thin film electrode has been studied in acid media by cyclic voltammetry and bulk electrolysis. The results have shown that in the potential region of water stability there can occur direct electron transfer reactions on BDD surface that result in electrode fouling due to the formation of a polymeric film on its surface. While during electrolyses in the potential region of water decomposition, indirect oxidation reactions can take place by electrogenerated active intermediates, probably hydroxyl radicals that can avoid electrode fouling. Depending on the values of applied current density, it is possible to obtain the partial oxidation of 3-MP to nicotinic acid or the complete combustion of 3-MP to CO₂.     

Electro-combustion of polyacrylates with boron-doped diamond anodes

The electro-combustion of water soluble polymeric contaminants like polyacrylates (PA) in aqueous acid solution using a boron-doped diamond (BDD) anode has been investigated by bulk electrolysis in 1 mol dm⁻³ HClO₄ under galvanostatic conditions in a wide range of PA concentrations and current densities. In all cases complete electro-combustion of PA has been achieved and this is the first successful report for the electro-combustion of soluble organic polymers.The experimental chemical oxygen demand (COD) and instantaneous current efficiency (ICE) values are well predicted from a theoretical model which suppose that the rate of electro-combustion of PA with electrogenerated active intermediates (probably hydroxyl radicals) is a fast reaction and is controlled by mass transport of PA towards the anode (concept of the “ideal anode” for electro-combustion).     

Removal of pesticide chlorobenzene by anodic degradation: Variable effects and mechanism

The oxidation of chlorobenzene (CB) was studied by electrochemical electrolysis using boron-doped diamond (BDD), PbO₂ or platine (Pt) as anode and graphite bar as cathode. The effect of applied current density, supporting electrolyte and initial pH value were also studied. The results demonstrated that BDD anode had the best effectiveness and accomplishment of electrochemical degradation of CB compared to PbO₂ and Pt anodes. For a current density of 20 mA/cm² and at pH = 3, the elimination of COD and TOC were about 97% and 98%, respectively, after 360 min of electrolysis with the BDD anode. Pseudo-first order kinetics appears to be the most appropriate to describe the degradation of chlorobenzene. The electrochemical mechanism of chlorobenzene on BDD was proposed based on the identified intermediates.     

Direct electrochemical oxidation of polyacrylates

A promising elimination treatment of non-biodegradable organic pollutants is the direct electro-oxidation. In this work has been proposed the electrochemical elimination of polyacrylates by using boron-doped diamond (BDD) as anodic material. The complete elimination of organic contaminants has been obtained and this is the first case of successful electrochemical treatment of polymeric and bio-refractory species. The tests of the electrochemical oxidation have been conducted at constant current conditions and a complete elimination of organic species has been reached. The decrease of the COD value with time follows the behaviour of an ideal anode as in the case of low molecular organic compounds.     

Indirect electrochemical oxidation of aniline in acid electrolyte with active oxygen species

Kinetics and selectivity of the aniline oxidation on a boron-doped diamond electrode and lead dioxide anode (Pb/PbO₂) in an acid electrolyte were studied under various generation conditions of active oxygen species. The resulting kinetic dependences can be described by a pseudo-first-order equation. The apparent rate constants of the process were determined for two electrolysis modes: direct anodic oxidation and oxidation with addition of hydrogen peroxide. UV spectroscopy was used to determine that the aniline destruction process occurs via formation of a number of intermediate products (benzoquinone, carboxylic acids). It was shown that the aniline destruction process can occur with a rather high efficiency (~80–90%) on the electrode types under study.     

Indirect electrochemical oxidation of aliphatic alcohols to carboxylic acids by active oxygen forms in aqueous media

Indirect electrochemical oxidation of aliphatic alcohols (butanol, hexanol, nonanol, decanol) to the corresponding carboxylic acids by active oxygen forms (AOFs) generated in situ in electrochemical cells from O₂, H₂O₂, H₂O is carried out in aqueous electrolyte using anodes of lead dioxide, a nickel oxide electrode, and boron-doped diamond electrode (BDDE). It is found that selectivity of the process of indirect electrosynthesis of carboxylic acids depends on the chemical nature of the anode material and structure of the initial alcohol and is determined by the conditions of AOF generation. Coupled electrosynthesis with simultaneous in situ generation of AOFs on the cathode and anode occurs more effectively with formation of the corresponding carboxylic acids.     

Electrochemical synthesis of ferrate in presence of ultrasound using boron doped diamond anodes

The use of an ultrasound processor is proposed to enhance the efficiency of the electrosynthesis of ferrates with boron-doped diamond anodes. The chemical dissolution of the iron powder used as raw material, due to the extreme pH on the nearness of the anode surface, improves the results significantly. The application of ultrasound during electrolyses, besides having a positive effect on the dissolution of the raw material, also favors the mass transport of iron species to the electrode surface, and thus its used enhances the efficiency of the process. The hydroxyl ion concentration and the current density also have a clear influence on the results: high current density favors iron dissolution and hydroxyl radical generation, whereas high hydroxyl ions concentration contributes to the stability of produced ferrate.     

用于有机物降解的电化学阳极材料

电化学氧化法可将难降解的有机物转化为可生化降解物质或直接矿化,具有操作简便,清洁能源,无二次污染等优点。本文介绍了电催化氧化机理最新进展,包括近年来所报道的各种电极材料直接或间接电氧化降解有机物的机制;回顾了近年来阳极材料的研究现状,以碳电极、金属电极和钛基形稳电极为主,包括各种新型电极的组成、降解性能及其钝化原因等,并对今后电氧化阳极材料及相关工艺的研究方向提出建议。     

Electrochemical oxidation of phenol at boron-doped diamond electrode. Application to electro-organic synthesis and wastewater treatment

The electrochemical behaviour of a synthetic boron-doped diamond thin film electrode (BDD) has been studied in acid media containing phenol using cyclic voltammetry and bulk electrolysis. The results have shown that in the potential region of water stability direct electron transfers can occur on BDD surface resulting in electrode fouling due to the formation of a polymeric film on its surface. During electrolysis in the potential region of oxygen evolution, complex oxidation reactions can take place due to electrogenerated hydroxyl radicals. Electrode fouling is inhibited under these conditions. Depending on the experimental conditions, the electrogenerated hydroxyl radicals can lead to the combustion of phenol or to the selective oxidation of phenol to benzoquinone. The experimental results have also been compared to a theoretical model that permits the prediction of the evolution with time of phenol concentration, during its combustion, or during its selective oxidation to benzoquinone.     

Integration of anodic and cathodic processes for the synergistic electrochemical production of peracetic acid

Efficient in-situ production of peracetic acid is an unreached milestone of electrochemical engineering. Previous attempts in the production of peracetic acid were focused either on the cathodic production of hydrogen peroxide and its further addition to acetic acid solutions or on the oxidation of a suitable raw material (v. g. acetic acid, acetaldehyde, ethanol). In the present work, the oxidation of acetic acid by a boron doped diamond (BDD) anode was integrated with the cathodic production of hydrogen peroxide using a carbon felt gas diffusion electrode. A marked synergistic effect (synergy coefficient of 192.0 ± 13.1%) is observed when the oxidation of acetic acid by hydroxyl radicals is performed together with the cathodic production of hydrogen peroxide. A maximum PAA production efficiency of 19.87% was obtained, a value much higher than previous works based on the oxidation of acetic acid by BDD anodes and approximately double the optimal value reported in studies based on the production of hydrogen peroxide.     

Electrochemical Oxidation of Sulfonamides with Boron-Doped Diamond and Pt Anodes

Electrochemical oxidation processes usually favored specific degradation pathways depending on anode materials. In this work, a series of sulfonamides (SNs) were degraded by electrochemical oxidation. Compared to Pt anodes (0.1567–0.1795 h⁻¹), degradation rates of SNs were much higher at boron-doped diamond (BDD) anodes (2.4290–13.1950 h⁻¹). However, the same intermediates were detected in the two anode systems. Due to the strong oxidizing ability of BDD anodes, a large amount of intermediates with high toxicities were initially generated and then finally reduced in the BDD anode systems, while the amount of intermediates continuously increased in the Pt anode systems. Additionally, SNs were degraded faster in Na₂SO₄ than NaH₂PO₄ electrolytes at BDD anodes, while they were similar at Pt anodes. This study demonstrated that the degradation pathways of SNs at BDD and Pt anodes were similar, but the evolutions of intermediate amounts and toxicities were different due to their varied oxidizing abilities.     

Indirect electrochemical oxidation of reverse osmosis membrane concentrates at boron-doped diamond electrodes

The treatment or disposal of concentrates generated from the filtrative treatment of water is rapidly becoming a factor of major environmental concern. This preliminary study discusses a novel approach in the abatement of reverse osmosis membrane retentate i.e. electrochemical oxidation. The recalcitrant organic constituents as well as the ammonia nitrogen in the retentate could be readily oxidised using boron-doped diamond electrodes. From the model fitted to these data, a constant removal rate and current efficiency was calculated. Analysis of the inorganic chlorinated species revealed that the oxidation mechanism was mainly due to the indirect oxidative action of electrogenerated hypochlorite.     

Direct and mediated electrochemical oxidation of ammonia on boron-doped diamond electrode

Direct (non-mediated) electrochemical oxidation of ammonia on boron-doped diamond (BDD) electrode proceeds mainly at high pH (> 8) via free ammonia (NH₃) oxidation. To enhance ammonia oxidation on BDD at low pH (< 8), where mainly ammonium (NH₄⁺) is present, oxidation of ammonia was mediated by active free chlorine. In this process, electro-generated in situ active chlorine rapidly reacts with ammonia instead of being further electro-oxidized to chlorate at the electrode surface. Thus, active chlorine effectively removes ammonia from an acidic solution, while the formation of by-products such as chlorate and possibly perchlorate is minimized.     

Anodic oxidation of organic pollutants: Anode fabrication,process hybrid and environmental applications

This review summarizes the recent progress in anodic oxidation of organic pollutant for water and wastewater treatment. It supplies the advances in anodes fabrication to improve the anodic performance by different modifications and preparation strategies, focusing on non-active anodes including boron-doped diamond (BDD), PbO₂, SnO₂ and Ti-based anode (e.g., Ti₄O₇, blue titanium oxide). Meanwhile, the tendency of anodic oxidation coupled or combined with other processes (adsorption, membrane separation, biological treatment and advanced oxidation process) for pretreatment or advanced treatment of organic pollutant is presented. Finally, anodic oxidation for environmental application is briefly described; several challenges need to be overcome and perspectives for future study are critically proposed.     

Electrocatalytic Oxidation of Organic Pollutants on Boron-Doped Diamond and Ti–Ru Oxide Anodes in Sulfate Medium

Electrochemical oxidation for degradation of industrial dye Methyl Orange in aqueous sulfate solutions with various electrocatalytic materials: boron-doped diamond electrode and electrode based on titanium and ruthenium oxides. The influence exerted by the main working parameters of electrolysis (current density, concentration of Methyl Orange, pH) on the discoloration efficiency and on the chemical oxygen demand (COD) was examined. It was shown that an increase in the current density and a decrease in the pollutant concentration improve the process efficiency. However, this leads to an increase in the specific electric energy consumption per unit mass of COD. It was found that the boron-doped diamond electrode is a more efficient electrocatalytic material, compared with electrode based on titanium and ruthenium oxides. At low concentrations of Methyl Orange (<50 mg L^–1), there exists the possibility in principle of using the electrode based on titanium and ruthenium oxides not only for discoloration, but also for making lower the COD level.     

Use of low current densities in electrolyses with conductive-diamond electrochemical — Oxidation to disinfect treated wastewaters for reuse

In the search for new disinfection technologies for reused water, in this work the effect of current density on the disinfection capability, during the electrolyses with conductive diamond anodes of the effluent of a municipal wastewater treatment plant was evaluated. It was found that this electrolytic technology can disinfect completely for current densities ranging from 1.3 to 130 A m^{− 2}, but the disinfection rate and chlorine speciation are significantly affected by particular current density applied. In order to avoid the occurrence of non desired species, the lower value of this range is proposed. In those conditions, complete disinfection can be obtained and hypochlorite and chloramines are the main species, not being produced chlorate, perchlorate or organo-chlorinates species.     

Electrochemical degradation of buprofezin insecticide in aqueous solutions by anodic oxidation at boron-doped diamond electrode

Buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazinan-4-one) is identified as a commonly used chemical with satisfactory biological activities against sucking insect pests, but its disposal causes serious environmental problems. This pesticide was treated by an electrolysis system using a boron-doped diamond (BDD) as anode and platinum as cathode. A number of experiments were run on a laboratory scale and the results are presented. The chemical oxygen demand (COD) measurement during the processing permitted the evaluation of the kinetic of organic matter decay and the instantaneous current efficiency. Different operating conditions and factors affecting the treatment process including current density, conductive electrolyte, pH, concentration of buprofezin, and time of electrolysis were studied and optimized. The best obtained conditions for COD removal on the BDD anode to degrade buprofezin solutions (COD₀ = 1,200 mg L^?1) include operating at 60 mA cm^?2 and 25 ± 3 °C. The high efficiency of this technology can be explained in terms of the direct electrooxidation at the BDD surface and the oxidation carried out by hydroxyl radicals (OH^?) and other electro-generated oxidants (Cl^?, ClO^?).     

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.     

Recent advances on boron doped diamond (BDD) electrode as cathode in organic and inorganic preparative electrotransformations

Although anodic oxidation reactions mediated by boron-doped diamond (BDD) electrodes have been broadly studied, research on cathodic conversion remains still scarce despite the favorable characteristics of this electrode for such application. A detailed survey of the recent literature about processes in which boron-doped diamond electrode has been employed in cathodic reactions is presented, including inorganic species (O₂, CO₂, nitrate, metaborate) and organic compounds (carbonyl, nitro groups and halogenated compounds).     

LSGMC5含量对于二甲醚燃料电池复合Ni-Fe阳极性能的影响

用浸渍法制备了掺杂不同质量分数的La0.8Sr0.2Ga0.8Mg0.15Co0.05O3-δ (LSGMC5)粉末的Ni8-Fe2-LSGMC5复合阳极, 并采用交流阻抗和直流极化技术考察了以氢气和二甲醚为燃气时该复合阳极的电化学性能及相应电池的功率输出特性. 结果表明, 在电极中掺入LSGMC5 粉末, 能显著地改善电极的形貌和电极/电解质界面结构, 减小欧姆电阻和极化电阻. 电极中LSGMC5 粉末含量对于氢气及二甲醚电化学氧化性能的影响显著不同. 以二甲醚为燃气时, 电极极化电阻随LSGMC5 粉末含量的增加而减小, 其中LSGMC5 掺杂量为30%的复合阳极具有最高的电化学性能, 相应电池在1073、1023、973 K 时的输出功率分别为1.00、0.61、0.40 W·cm-2; 以氢气为燃气时, LSGMC5 掺杂量为20%的复合阳极具有最好的电化学性能, 随着LSGMC5 掺杂量的进一步增加, 电极极化电阻显著增大.