The Strategies Towards Electrochemical Generation of Aryl Radicals.

The advancement in electrochemical techniques has unlocked a new path for achieving unprecedented oxidations and reductions of aryl radical precursors in a controlled and selective manner. This approach facilitates the construction of aromatic carbon-carbon and carbon-heteroatom bonds. In light of the green merits and the growing importance of this technique in aryl radical chemistry, this review aims to provide an overview of the recent advance in the electrochemical generation of aryl radicals organized by the aryl radical precursor type, with a focus on the substrate scope, limitation, and underlying mechanism, thereby inspiring future work on electrochemical aryl radical generation.

Cyclic Voltammetry of C.I. Disperse Orange 62 in an Aqueous Electrolyte.

Disperse dyes are an important group of colorants for dyeing polyester fibers. Approximately 30.000 tons of disperse dyes are released into the waste water annually from spent dyebaths. Therefore, methods for decolorizing such dyes are of general interest. The reductive after-treatment of disperse dyes using reducing agents, such as Na2S2O4, is a widely used process to improve rub fastness through dye reduction. Electrochemical dye reduction could be an alternative process for reductive dye treatment. In this work C.I. Disperse Orange 62 was used as a representative dye to study the direct cathodic reduction of a disperse dye with cyclic voltammetry. As anticipated for dispersed organic matter, relatively low current densities were observed, which strongly depend on the state of dispersion of the dye. The current density was increased by using dispersions prepared through dye precipitation from DMF solution and by the use of N-cetyl-N,N,N,-trimethyl-ammonium bromide as a cationic surfactant. The results demonstrate the successful cathodic reduction of a dispersed organic dye; however, the low solubility of the reaction products in the aqueous electrolyte hinders an efficient cathodic dye reduction.

Research progress on using biological cathodes in microbial fuel cells for the treatment of wastewater containing heavy metals.

Various types of electroactive microorganisms can be enriched to form biocathodes that reduce charge-transfer resistance, thereby accelerating electron transfer to heavy metal ions with high redox potentials in microbial fuel cells. Microorganisms acting as biocatalysts on a biocathode can reduce the energy required for heavy metal reduction, thereby enabling the biocathode to achieve a lower reduction onset potential. Thus, when such heavy metals replace oxygen as the electron acceptor, the valence state and morphology of the heavy metals change under the reduction effect of the biocathode, realizing the high-efficiency treatment of heavy metal wastewater. This study reviews the mechanisms, primary influencing factors (e.g., electrode material, initial concentration of heavy metals, pH, and electrode potential), and characteristics of the microbial community of biocathodes and discusses the electron distribution and competition between microbial electrodes and heavy metals (electron acceptors) in biocathodes. Biocathodes reduce the electrochemical overpotential in heavy metal reduction, permitting more electrons to be used. Our study will advance the scientific understanding of the electron transport mechanism of biocathodes and provide theoretical support for the use of biocathodes to purify heavy metal wastewater.

Rational design of electrocatalytic system to selective transform nitrate to nitrogen.

Nitrate (NO3-) is one of the most common pollutants in natural bodies of water and as such threatens both human health and the safety of aquatic environment. There are efficient electrochemical techniques to directly remove NO3-, but inexpensive, selective and electrocatalytic strategies to eliminate NO3- by converting it into benign nitrogen (N2) remain challenging. This work studied Cu particles that were formed directly on a Ni foam (Cu-NF) and evaluated their electrocatalytic NO3- reduction performance. The use of carbon nanotubes (CNT) functionalized with titanium suboxides (TiSO) as the anode facilitated the generation of active chlorine species that had a key role in the removal of NH4+. An electrochemical system that integrated a Cu-NF cathode with a TiSO-CNT anode could remove 88.5% of NO3- with a >99% N2 selectivity when operated over 6 h (4.1 × 10-4 h-1) at a potential of -1.2 V vs Ag/AgCl. Because the chloride ions are very common in natural sources of water, this technique offers a sustainable and environmentally friendly approach for the removal of NO3- from contaminated water sources.

Electroreductively Induced Radicals for Organic Synthesis.

Organic electrochemistry has attracted tremendous interest within the novel sustainable methodologies that have not only reduced the undesired byproducts, but also utilized cleaner and renewable energy sources. Particularly, oxidative electrochemistry has gained major attention. On the contrary, reductive electrolysis remains an underexplored research direction. In this context, we discuss advances in transition-metal-free cathodically generated radicals for selective organic transformations since 2016. We highlight the electroreductive reaction of alkyl radicals, aryl radicals, acyl radicals, silyl radicals, fluorosulfonyl radicals and trifluoromethoxyl radicals.

Electrosynthetic C-O Bond Activation in Alcohols and Alcohol Derivatives.

Alcohols and their derivatives are ubiquitous and versatile motifs in organic synthesis. Deoxygenative transformations of these compounds are often challenging due to the thermodynamic penalty associated with the cleavage of the C-O bond. However, electrochemically driven redox events have been shown to facilitate the C-O bond cleavage in alcohols and their derivatives either through direct electron transfer or through the use of electron transfer mediators and electroactive catalysts. Herein, a comprehensive overview of preparative electrochemically mediated protocols for C-O bond activation and functionalization is detailed, including direct and indirect electrosynthetic methods, as well as photoelectrochemical strategies.

Low Platinum-Content Electrocatalysts for Highly Sensitive Detection of Endogenously Released H2O2.

The commercial viability of electrochemical sensors requires high catalytic efficiency electrode materials. A sluggish reaction of the sensor's primary target species will require a high overpotential and, consequently, an excessive load of catalyst material to be used. Therefore, it is essential to understand nanocatalysts' fundamental structures and typical catalytic properties to choose the most efficient material according to the biosensor target species. Catalytic activities of Pt-based catalysts have been significantly improved over the decades. Thus, electrodes using platinum nanocatalysts have demonstrated high power densities, with Pt loading considerably reduced on the electrodes. The high surface-to-volume ratio, higher electron transfer rate, and the simple functionalisation process are the main reasons that transition metal NPs have gained much attention in constructing high-sensitivity sensors. This study has designed to describe and highlight the performances of the different Pt-based bimetallic nanoparticles and alloys as an enzyme-free catalytic material for the sensitive electrochemical detection of H2O2. The current analysis may provide a promising platform for the prospective construction of Pt-based electrodes and their affinity matrix.

Cathodic generation of reactive (phenylthio)difluoromethyl species and its reactions: mechanistic aspects and synthetic applications.

The cathodic reduction of bromodifluoromethyl phenyl sulfide (1) using o-phthalonitrile as a mediator generated the (phenylthio)difluoromethyl radical, which reacted with α-methylstyrene and 1,1-diphenylethylene to provide the corresponding adducts in moderate and high yields, respectively. In contrast, chemical reduction of 1 with SmI2 resulted in much lower product yields. The detailed reaction mechanism was clarified based on the cathodic reduction of 1 in the presence of deuterated acetonitrile, CD3CN.

First example of organocatalysis by cathodic N-heterocyclic carbene generation and accumulation using a divided electrochemical flow cell.

In this paper we present the first electrochemical generation of NHC carried out in a divided flow cell. The flow cell operated in the recycle mode. The need for a divided cell derived from the anodic electroactivity of the electrogenerated carbene. In order to have NHC accumulation in the catholyte, the Nafion membrane (cell separator) was pretreated with an alkaline solution. The formation of NHC was quantified as its reaction product with elemental sulfur. The NHC was successfully used as organocatalyst in two classical umpolung reactions of cinnamaldehyde: its cyclodimerization and its oxidative esterification.

Prospects of Using Pseudobrookite as an Iron-Bearing Mineral for the Alkaline Electrolytic Production of Iron.

The alkaline electrolytic production of iron is gaining interest due to the absence of CO2 emissions and significantly lower electrical energy consumption when compared with traditional steelmaking. The possibility of using an iron-bearing pseudobrookite mineral, Fe2TiO5, is explored for the first time as an alternative feedstock for the electrochemical reduction process. To assess relevant impacts of the presence of titanium, similar electroreduction processes were also performed for Fe2TiO5·Fe2O3 and Fe2O3. The electroreduction was attempted using dense and porous ceramic cathodes. Potentiostatic studies at the cathodic potentials of -1.15--1.30 V vs. an Hg|HgO|NaOH reference electrode and a galvanostatic approach at 1 A/cm2 were used together with electroreduction from ceramic suspensions, obtained by grinding the porous ceramics. The complete electroreduction to Fe0 was only possible at high cathodic polarizations (-1.30 V), compromising the current efficiencies of the electrochemical process due to the hydrogen evolution reaction impact. Microstructural evolution and phase composition studies are discussed, providing trends on the role of titanium and corresponding electrochemical mechanisms. Although the obtained results suggest that pseudobrookite is not a feasible material to be used alone as feedstock for the electrolytic iron production, it can be considered with other iron oxide materials and/or ores to promote electroreduction.

Enhancement in Cathodic Redox Reactions of Single-Chambered Microbial Fuel Cells with Castor Oil-Emitted Powder as Cathode Material.

Microbial fuel cell (MFC) would be a standalone solution for clean, sustainable energy and rural electrification. It can be used in addition to wastewater treatment for bioelectricity generation. Materials chosen for the membrane and electrodes are of low cost with suitable conducting ions and electrical properties. The prime objective of the present work is to enhance redox reactions by using novel and low-cost cathode catalysts synthesized from waste castor oil. Synthesized graphene has been used as an anode, castor oil-emitted carbon powder serves as a cathode, and clay material acts as a membrane. Three single-chambered MFC modules developed were used in the current study, and continuous readings were recorded. The maximum voltage achieved was 0.36 V for a 100 mL mixture of domestic wastewater and cow dung for an anodic chamber of 200 mL. The maximum power density obtained was 7280 mW/m2. In addition, a performance test was evaluated for another MFC with inoculums slurry, and a maximum voltage of 0.78 V and power density of 34.4093 mW/m2 with an anodic chamber of 50 mL was reported. The present study's findings show that such cathode catalysts can be a suitable option for practical applications of microbial fuel cells.

Electrochemical Arylation of Aldehydes, Ketones, and Alcohols: from Cathodic Reduction to Convergent Paired Electrolysis.

Arylation of carbonyls, one of the most common approaches toward alcohols, has received tremendous attention, as alcohols are important feedstocks and building blocks in organic synthesis. Despite great progress, there is still a great gap to develop an ideal arylation method featuring mild conditions, good functional group tolerance, and readily available starting materials. We now show that electrochemical arylation can fill the gap. By taking advantage of synthetic electrochemistry, commercially available aldehydes (ketones) and benzylic alcohols can be readily arylated to provide a general and scalable access to structurally diverse alcohols (97 examples, >10 gram-scale). More importantly, convergent paired electrolysis, the ideal but challenging electrochemical technology, was employed to transform low-value alcohols into more useful alcohols. Detailed mechanism study suggests that two plausible pathways are involved in the redox neutral α-arylation of benzylic alcohols.

Relationship between bioelectrochemical copper migration, reduction and electricity in a three-chamber microbial fuel cell.

Microbial fuel cells (MFCs) can remove and recover metals in wastewater; however, there are relatively few studies of metal removal from soil by MFCs. In this study, we developed a three-chamber soil MFC consisting of an anode, contaminated soil, and cathode chamber to remove heavy metals from soil. The performance of the soil MFC was investigated by assessing the relationships among current, voltage, and Cu migration, and reduction. The developed soil MFC successfully reduced and removed Cu, and the Cu removal efficiency in the cathode surpassed 90% after only 7 days of operation. External resistance had a remarkable effect on the performance of the soil MFC which was depended on cathodic polarization. The pH in the cathode also depended on the external resistance. Lower external resistance were associated with lower pH values, higher Cu removal efficiencies, and greater amounts removed in the cathode. Based on sequential fractionation, the acid-extractable and reducible fractions were the main fractions that migrated within the three-chamber soil MFC. Enhancing the voltage output in the three-chamber soil MFC by increasing the external resistance promoted Cu migration, enriched Cu near the cathode, and facilitated Cu removal. Therefore, the developed three-chamber soil MFC not only supports heavy metal migration from soil towards the cathode, but can also realize reduction of heavy metals in the cathode by adjusting the current or voltage generated by the soil MFC.

Catalyst-Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro-Induced Radical Formation.

Electro-induced reduction of redox active esters and N-phthalimidoyl oxalates derived from naturally abundant carboxylic acids and alcohols provides a sustainable and inexpensive approach to radical formation via undivided electrochemical cells. The resulting radicals are trapped by an electron-poor olefin or hydrogen atom source to furnish the Giese reaction or reductive decarboxylation products, respectively. A broad range of carboxylic acid (1°, 2°, and 3°) and alcohol (2° and 3°) derivatives are applicable in this catalyst-free reaction, which tolerated a diverse range of functional groups. This method features simple operation, is a sustainable platform, and has broad application.

Electrochemical Arylation of Electron-Deficient Arenes through Reductive Activation.

An electrochemical method has been developed to achieve arylation of electron-deficient arenes through reductive activation. Various electron-deficient arenes and aryldiazonium tetrafluoroborates are amenable to this transformation within the conditions of an undivided cell, providing the desired products in up to 92 % yield. Instead of preparing diazonium reagents, these reactions can begin from anilines, and they can be carried out in one pot. Electron paramagnetic resonance studies indicate that cathodic reduction of quinoxaline occurs using the transformation. Moreover, cyclic voltammetry indicates that both quinoxaline and aryl diazonium salt have relatively low reduction potentials, which suggests they can be activated through reduction during the reaction.

Voltammetric analysis of dantrolene and its active metabolite with indomethacin in rat plasma.

AIM: Differential pulse polarography was used for the concurrent analysis of the coadministered dantrolene (DAN) and indomethacin (IND) in plasma. MATERIALS & METHODS: DAN and IND, Hanging mercury drop electrode and Britton-Robinson buffer at pH 5 were used. In plasma, cathodic reduction of DAN nitro group and its active metabolite at -0.2 V was done. IND was analyzed after carbonyl group reduction at -1.1 V. RESULTS: Drugs determination in rat plasma with good recoveries and low limit of quantitation was done. Application to trace analysis of drugs in rat plasma was done with Cmax and Tmax determination. CONCLUSION: This technique shows high sensitivity, simplicity and low cost. The method is US FDA validated and it is applicable to human level.

Electrochemically modified Corey-Fuchs reaction for the synthesis of arylalkynes. The case of 2-(2,2-dibromovinyl)naphthalene.

The electrochemical reduction of 2-(2,2-dibromovinyl)naphthalene in a DMF solution (Pt cathode) yields selectively 2-ethynylnaphthalene or 2-(bromoethynyl)naphthalene in high yields, depending on the electrolysis conditions. In particular, by simply changing the working potential and the supporting electrolyte, the reaction can be directed towards the synthesis of the terminal alkyne (Et4NBF4) or the bromoalkyne (NaClO4). This study allowed to establish that 2-(bromoethynyl)naphthalene can be converted into 2-ethynylnaphthalene by cathodic reduction.

Electrochemistry for the Generation of Renewable Chemicals: One-Pot Electrochemical Deoxygenation of Xylose to δ-Valerolactone.

In this study, the electrochemical conversion of xylose to δ-valerolactone via carbonyl intermediates is demonstrated. The conversion was achieved in aqueous media and at ambient conditions. This study also demonstrates that the feedstock for production of renewable chemicals and biofuels through electrochemistry can be extended to primary carbohydrate molecules. This is the first report on a one-pot electrochemical deoxygenation of xylose to δ-valerolactone.

Cathodic reductive coupling of methyl cinnamate on boron-doped diamond electrodes and synthesis of new neolignan-type products.

The electroreduction reaction of methyl cinnamate on a boron-doped diamond (BDD) electrode was investigated. The hydrodimer, dimethyl 3,4-diphenylhexanedioate (racemate/meso = 74:26), was obtained in 85% yield as the major product, along with small amounts of cyclic methyl 5-oxo-2,3-diphenylcyclopentane-1-carboxylate. Two new neolignan-type products were synthesized from the hydrodimer.

Stereoselective cathodic synthesis of 8-substituted (1R,3R,4S)-menthylamines.

The electrochemical generation of menthylamines from the corresponding menthone oximes equipped with an additional substituent in position 8 is described. Due to 1,3-diaxial interactions a pronounced diastereoselectivity for the menthylamines is found.