Relevance of gaseous flows in electrochemically assisted soil thermal remediation

Treatment of polluted soil is one of the priorities in the search of a more sustainable planet. Electrochemically assisted soil remediation has been considered a good option for removing organic contaminants contained in soil, including the removal of volatile organic compounds, associated with gaseous streams produced during the treatment. Also, recently, electrochemical gas treatment technologies have been appointed as promising for the treatment of volatile organic compounds. In this work, we review the current opinion about the most recent studies in both areas. The first section focuses on the production of gaseous compounds during soil remediation by conventional and electrochemical systems. The second section describes the recent progress in the integration of adsorption and absorption with electrochemical processes. Finally, we discuss the holistic application of assisted electrochemical technologies in soil remediation, considering also emerging processes recently published in the literature.     

Use of a standard system to evaluate the matrix effect on the treatment of a solution from atrazine contaminated soils

The influence of humic substances on the electrochemical treatment of solutions resulting from the remediation of atrazine contaminated soil has been investigated. In particular the effect on the hydrogen peroxide production stage and the effect on the hydroxyl radical oxidation treatment have been separately studied. In order to quickly assess the possible inhibition of the removal, an inorganic system has been adopted as a standard system. The results confirm the validity of electrochemical technologies also for the treatment of a real effluent where a matrix effect is expected since the organic matter content affects only the hydrogen peroxide production.     

Cationic intermediates in oxidative addition reactions of Cl2 to [PtCl2(cis-1,4-DACH)

Oxidative addition and reductive elimination are fundamental processes in transition-metal chemistry. New interest in this field has been generated by the exploitation of platinum(IV) complexes as antitumor drugs. The two extra ligands can be used to render these species more resistant to attack by biological nucleophiles compared to their platinum(II) counterparts, to anchor additional pharmacologically active moieties, or, finally, to target the drug to specific sites by conferring responsiveness to some type of chemotaxis. On the other hand, platinum(IV) species are considered to be prodrugs and to require reduction to Pt(II) to become active. Thus, reductive elimination promoted by biological reducing agents becomes an important issue and it too could be exploited for targeting purposes. In this paper, we investigated the oxidation step in more detail and shown that, independent of the solvent used, a solvent molecule assists the reaction by entering in a trans position with respect to the attacking oxidant. In the case of bifunctional solvent molecules, such as dimethylsulfoxide, both S- and O-coordinated species are formed, the latter being thermodynamically favored. The substitution of the axially coordinated solvent molecule by a free chloride ion is found to be quite slow in organic solvents, as well as in water. It is also shown that the intermediate solvato-species can be exploited for binding just one molecule of another substrate in the axial position.     

Enhanced functionality for donor-acceptor oligothiophenes by means of inclusion of BODIPY: synthesis, electrochemistry, photophysics, and model chemistry

We have synthesized several new push-pull oligothiophenes based on the boron dipyrromethene (BODIPY) moiety as the electron acceptor and the more well-known oligothiophenes substituted with N,N-dialkylamino functions to enhance their electron-donor ability. A complete characterization of the electronic properties has been carried out; it consists of their photophysical, electrochemical, and vibrational properties. The compounds have been studied after chemical treatment with acids and after oxidation. In this regard, they can be termed as NIR dyes and amphoteric redox electroactive molecules. We have described the presence of dual fluorescence in these molecules and fluorescence quenching either by energy transfer or, in the push-pull molecules, by electron exchange. The combination of electrochemical and proton reversibility along with the interesting optical properties of the new species offer an interesting platform for sensor and material applications.     

Industrial solution contaminated by polyacrylates: their elimination by electrochemical combustion

The electrochemical combustion of polyacrylates was studied through both direct and indirect oxidation. The obtained results indicate the non elimination of the polyacrylates with the direct oxidation, while the indirect oxidation with NaCl completely eliminates these organic compounds. In the last case the effects of different initial concentrations of NaCl, anode materials and current densities was studied.     

What happens to inorganic nitrogen species during conductive diamond electrochemical oxidation of real wastewater?

This work describes the oxidation of caffeine, metoprolol, SMX and progesterone in real wastewater in terms of inorganic nitrogen speciation and help clarify the mechanisms that affect inorganic nitrogen species as final products. In synthetic solutions containing ammonium or nitrate ions, it has been confirmed that reduction of nitrates is a very favored process while oxidation of ammonium is negligible. Role of chloride is demonstrated to be important in the formation of chloramines, as well. These results allow the clarification of the production of nitrates as main products of the oxidation of organic chemicals and the occurrence of ammonium and chloramines in the reaction media, as well as the depletion of nitrogen by gaseous nitrogen production. Results are of a great relevance to interpret the mechanisms proposed in the literature for the treatment of organic wastes by conductive diamond electrochemical oxidation.     

有机电化学合成简谈

本文简要介绍了有机电化学合成的体系,研究方法和技术及主要特征。以C=C类物质为例介绍了有机电化学合成中的各类反应,并以己二腈的电合成为例介绍了相应的工业化应用。试图以CO2的电化学固定利用为例介绍了有机电化学合成的研究动向。     

Electroanalytical measurements without electrolytes: Conducting polymers as probes for redox titration in non-conductive organic media

Electroanalytical methods have been applied only in conducting media. An application of conducting polymers allows to overcome this limitation. If such material is in electrochemical equilibrium with dissolved redox active species, its electrical conductivity depends on the redox potential of these species. Therefore, conductometric measurements with conducting polymers can provide about the same information as classical redox electrodes. The approach was applied for redox titration. Equivalent points obtained by this titration in aqueous and organic electrolytes were identical. Then the approach was applied for determination of bromine number by redox titration in non-conducting organic phase.     

Deciphering the activation sequence of ferrociphenol anticancer drug candidates

The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions.     

Plasma reduction of bronze corrosion developed under long-term artificial ageing

Reference Cu-based alloy with chemical composition and micro-chemical structure similar to that of ancient alloys has been used for carrying out the artificial long-term degradation test based on chloride enriched soil (chemical + soil) degradation. The results show that such degradation procedure produces natural like “patinas” as the ones grown on archaeological artefacts, from a chemical, structural and micro-morphological point of view. Glow discharge plasma technique has been employed for the treatment of the as-corroded bronze coupons. The gradual elimination of chloride-containing corrosion products in favour of the formation of more stable species and even the complete reduction back to copper has been observed. The chemical and metallurgical features have been determined by combined use of different analytical techniques such as scanning electron microscopy with energy dispersive X-ray micro-analysis (SEM-EDS), X-ray diffraction (XRD) and optical microscopy.     

Sequential electrochemical/biological treatment for the removal of 2,6-dichlorophenol from synthetic wastewater

The paper examines the effect of chloride on the oxidation of 2,6-dichlorophenol (DCP) performed at TiO2/RuO2 DSA anodes, which are specific catalysts for chlorine evolution. The results indicate that chlorine/hypochlorite originating from chloride oxidation in certain favourable conditions reacts with the organic substrate at the diffusion layer near the anode, accelerating the mass transfer of the reactant towards the electrode surface. When the bulk concentration of organic substrate has become very low, the oxidising species can accumulate in the bulk solution where the accomplishment of the oxidation of residual reactant and of its intermediates takes place. Solutions which also contained glucose were electrolysed in order to verify the high level of selectivity of DCP oxidation with respect to a biodegradable substrate: glucose was found to be unchanged up to nearly complete elimination of DCP. The toxicity of the solution was sufficiently reduced to reach values compatible with the subsequent biological treatment.     

Bubbles pinned on electrodes: Friends or foes of aqueous electrochemistry?

Electrochemists and engineers regard adherent gas bubbles as redox-inactive and therefore blocking entities. Adhesion of bubbles at electrodes generally carries an energy penalty. But this is not always the case: bubbles pinned on an electrode surface initiate the oxidation of water-soluble species under conditions where such reactions would normally be considered impossible. Here we critically review the recent literature that is beginning to unveil the novel concept of on-water electrochemistry. Harnessing electrochemical reactivity of the water–gas–electrode interface has the potential to become a game-changer in organic electrosynthesis, accelerating the transition toward a sustainable chemical industry by simplifying the direct integration of renewable electricity into the production of commodity chemicals.     

阿霉素的光谱电化学研究

利用循环伏安、紫外可见光谱电化学、荧光光谱电化学、圆二色光谱电化学等方法研究了阿霉素(ADM)在石墨电极上的电化学行为.结果发现,阿霉素在+0.2～+0.7V和-0.2～-0.7V范围内分别出现一对氧化还原峰.正电位下,蒽环上的酚羟基发生单电子氧化,并伴随后续化学反应.负电位范围内,阿霉素经历ECE电极反应过程,即蒽醌经单电子还原生成半醌自由基,半醌可发生不可逆的化学反应,脱去配氧糖基,转变为7-去氧柔毛霉醌(7-deoxyadriamycinone),后者在更负的电位下形成一对可逆的新的氧化还原峰.     

Electrochemical dehydrogenative N–H/N–H coupling reactions

The N–N bond is present in many important organic compounds, such as hydrazines, pyrazoles, azos, etc. Many methods based on transition metal catalyzed N–N coupling or functionalization of hydrazine have been reported for the synthesis of N–N containing organic compounds. In recent years, electrochemical dehydrogenative N–H/N–H coupling has become a powerful tool for the construction of N–N bearing organic compounds. The electrochemical methods employ electrons as traceless redox reagents instead of chemicals and produce hydrogen as the only byproduct. In this review, we summarize the recent advances in the electrochemical dehydrogenative N–H/N–H coupling reactions with focus on the mechanistic insights and synthetic applications of these transformations.     

Electrochemical reduction of CO2 and degradation of KHP on boron-doped diamond electrodes in a simultaneous and enhanced process

A BDD-BDD system was developed in the simultaneous conversion of CO₂ and wastewater purification in one electrochemical cell.     

Interest of micro-reactors for the implementation of advanced electrocatalytic oxidation with boron-doped diamond anode for wastewater treatment

Boron-doped diamond (BDD) anode has attracted great attention in the last two decades for its surpassing performance in the advanced electro-oxidation treatment of wastewater and disinfection. Due to the heterogeneous-like oxidation of organic pollutants, more suitable electrochemical reactor designs have been more recently proposed for optimal degradation and mineralization with BDD anode. Microfluidic reactors have emerged as a promising alternative by implementing submillimetric interelectrode gaps in flow-by or flow-through parallel-plate systems. Micro-reactors allow intensifying the mass transport of species toward the electrode while reducing the energy consumption and avoiding the addition of supporting electrolytes. The principle and main influencing operating parameters have been discussed in this review. Perspectives of the reactive electro-mixing reactor could permit the combination of micro-reactors with macro-reactors by increasing the treatment capacity while limiting the clogging effect. Further researches are required to overcome the drawbacks of micro-reactors and to benefit from electro-precipitation phenomena for the recovery of value-added compounds.     

Directing transition metal-based oxygen-functionalization catalysis

This review presents the recent progress of oxygen functionalization reactions based on non-electrochemical (conventional organic synthesis) and electrochemical methods. Although both methods have their advantages and limitations, the former approach has been used to synthesize a broader range of organic substances as the latter is limited by several factors, such as poor selectivity and high energy cost. However, because electrochemical methods can replace harmful terminal oxidizers with external voltage, organic electrosynthesis has emerged as greener and more eco-friendly compared to conventional organic synthesis. The progress of electrochemical methods toward oxygen functionalization is presented by an in-depth discussion of different types of electrically driven-chemical organic synthesis, with particular attention to recently developed electrochemical systems and catalyst designs. We hope to direct the attention of readers to the latest breakthroughs of traditional oxygen functionalization reactions and to the potential of electrochemistry for the transformation of organic substrates to useful end products.

This review presents the recent progress of oxygen functionalization catalysis via non-electrochemical (conventional organic synthesis) and electrochemical routes.     

Electrochemical Detection of Gunshot Residue for Forensic Analysis: A Review

Current demands for detection of Gunshot Residue (GSR) require a reliable and rapid decentralized detection system with high sensitivity and specificity. This article reviews the use of electrochemical devices for GSR detection over the last 35 years and highlights recent advances associated with the demands of GSR field detection such as portability, speed, cost and power. Anodic stripping voltammetry (ASV) has been widely implemented for the detection of the metallic components of GSR at a variety of working electrodes. Efforts toward the detection of the organic components of GSR have also been reported using cyclic‐ and square‐wave voltammetry. The simultaneous detection of both organic and inorganic GSR constituents has recently been examined to increase the overall information content in a single voltammetric scan. As well as this, exploitation of screen‐printing fabrication allows replacement of conventional electrochemical cells with easy‐to‐use sensor strips Sampling methods for electrochemical GSR analysis are also advancing from acid washes or swabs to simpler abrasive methods which integrate sampling and analysis obviating the need for intermediate processing steps. The latest direction of electrochemical detection of GSR involves chemometric treatment to evaluate data allowing for more objective conclusions and increasing the automation of the system. These advances indicate great promise for investigating firearm‐related crimes, and bring significant changes to the detection of GSR making electroanalysis a powerful tool for decentralized forensic analysis.     

流动注射-电化学氧化法测定水体化学需氧量

采用硼掺杂金刚石(Boron-doped diamond,BDD)薄膜电极为工作电极,利用流动注射分析方法测定水体化学需氧量(COD),根据水样中有机物组分在工作电极表面氧化消耗的电量(Qoxidation)测定样品的COD值。考察了一些基本参数包括载液、工作电位、流速对检测信号的影响并选定了最佳检测条件。在最佳检测条件下,本法检测COD的线性范围为2.5~120 mg/L,检出限为1 mg/L。用该法测定化工厂和食品厂废水的COD值,相对标准偏差和回收率分别在2.4%~4.8%和96%~106%之间,且检测结果与国家标准方法(CODcr法)有良好的一致性。     

Sebacic acid as corrosion inhibitor for hot-dip galvanized (HDG) steel in 0.1 M NaCl

The potential of sebacic acid as a corrosion inhibitor for hot-dip galvanized steel in 0.1 M NaCl solution has been investigated. Different concentrations of the organic acid have been tested in order to understand the inhibition mechanism of the compound. The electrochemical test revealed a competitive mechanism between the dissolution of the metal in the acidified solution and the inhibition provided by the dicarboxylic species. The formation of a whitish layer consisting of zinc carboxylates and corrosion products was proved by means of scanning electron microscopy (SEM) investigation combined with Fourier transform infrared (FT-IR) analysis. A bidentate bridging coordination between the Zn(II) and the carboxylic species is suggested.