Electroreduction of aliphatic chlorides at silver cathodes in water

Scialdone, Onofrio; Guarisco, Chiara; Galia, Alessandro; Herbois, Rudy

doi:10.1016/j.jelechem.2010.01.018

Cited by 68 publications

(51 citation statements)

References 48 publications

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Section: Introductionmentioning

confidence: 91%

“…Reduction will not lead to a complete mineralization, but to a complete dehalogenation, with a possible formation of double bonds. This has been proven for organic halides with one [3,4], two [5,6], three [7], four [8] or six [9] halogen atoms in their structure.Dehalogenation reactions of halogen-alkanes have been studied by direct and indirect electrochemical reductions and classical kinetics. The electrochemical redox processes can be divided into two categories: direct (heterogeneous) and indirect or mediated (homogeneous) ones.…”

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confidence: 91%

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Disposal of Poisonous Organic Halides by Using the Electrochemical Method: DFT Simulation

Spataru¹,

Fernández²,

Sista³

et al. 2016

ChemJMold

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Abstract. Geometry optimizations at the UBP86/6-311++G** level of electronic structure theory have been performed for DDT, β-hexachlorocyclohexane, and heptachlor organic polychlorides as well for their positive and negative ions. The HOMO composition of these neutral molecules show no participation of the carbon-chlorine atomic orbitals, while LUMO of the calculated molecules include a major contribution of the anti-bonding character atomic orbitals from the two or three carbon-chloride bonds of each calculated molecule. Consequently, the negative ions were the most sensitive structure during the geometry optimization, showing the carbon-chloride bonds cleaving during the electronic structure calculations. Further geometry optimization of the obtained neutral intermediate molecules after the fi rst and second reducing by two electrons show that the electrochemical dehalogenation of the organic poychlorides is sequential.Keywords: poisonous pesticides, organic chlorides, electrochemistry, DFT, carbon-chloride bonds. IntroductionThe electrochemical method for disposal of halogenated organic compounds leads to complete mineralization of organic halides. Generally, the electro-reductive treatments using new, improved electrochemical sensors, lead to partial recovery/recycling of chemicals, are regarded as an advantageous [1]. Methods of chemical and electro-chemical oxidation applied to organic pollutants attain, in most cases, a complete mineralization, being considered to have highenergy requirements [2]. Reduction will not lead to a complete mineralization, but to a complete dehalogenation, with a possible formation of double bonds. This has been proven for organic halides with one [3,4], two [5,6], three [7], four [8] or six [9] halogen atoms in their structure.Dehalogenation reactions of halogen-alkanes have been studied by direct and indirect electrochemical reductions and classical kinetics. The electrochemical redox processes can be divided into two categories: direct (heterogeneous) and indirect or mediated (homogeneous) ones. Direct electrochemical reduction involves electrons accepted directly by the analyte from the cathode surface, while indirect electrochemical reduction occurs between the analyte and an electrogenerated species, which serves as catalyst. Some authors use the term "mediator" as an alternative for catalyst [1]. The catalyst can exist in the electrolyte solution or can be immobilized on the electrode surface, namely CME's or chemically modifi ed electrodes [1,10]. By modifying the surface of the electrodes by adsorption of molecules or ions, the surface reactivity and slow kinetics can be overcome [10].Mechanistically, the halogen atoms are removed in a successive fashion, along with a two electron transfer at more and more cathodic (negative) potentials. This has been proven for polyhalogenated aromatics [11] and remains under question for polyhalogenated aliphatics. The diffi culty of attaining suffi ciently cathodic potentials would explain why complete dehalogenation does not alway...

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Section: Introductionmentioning

confidence: 91%

mentioning

confidence: 91%

Disposal of Poisonous Organic Halides by Using the Electrochemical Method: DFT Simulation

Spataru¹,

Fernández²,

Sista³

et al. 2016

ChemJMold

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“…For this reason, the electrochemical reductive cleavage of carbon-halogen bonds in organic compounds, with the particular focus on volatile organic halides, has been mainly studied and developed in the last decades [10][11][12][13] being the subject of numerous studies in aqueous [14][15][16], non aqueous [17][18][19] and mixed solvents [13,20]. The great interest for this process is due to its important role in some environmental applications, such as the abatement of volatile polychlorinated organic compounds, a group of pollutants having hazardous effects on living beings and out of the scope of most EAOPs.…”

Section: Introductionmentioning

confidence: 99%

Rapid screening of silver nanoparticles for the catalytic degradation of chlorinated pollutants in water

Lugaresi

Perales-Rondón

Minguzzi

et al. 2015

Applied Catalysis B: Environmental

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Please cite this article as: O. Lugaresi, J.V. Perales-Rondón, A. Minguzzi, J. SollaGullón, S. Rondinini, J.M. Feliu, C.M. Sánchez-Sánchez, Rapid screening of silver nanoparticles for the catalytic degradation of chlorinated pollutants in water, Applied Catalysis B, Environmental (2014), http://dx.doi.org/10. 1016/j.apcatb.2014.08.030 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. We suggest the proper size range and the presence of abundant superficial defective sites, such as steps or kinks, as the main reasons for Ag NPs C1 exhibiting the best overall catalytic performance in trichloromethane electrochemical reduction.

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“…Among the various methods, electroreductive hydrodehalogenations are very attractive because of their mild conditions, the possible production of value added substances, the rather good conversion yields and low energy consumptions thanks to the use of specific metallic (e.g. Ag, Pd, Cu, Pt) [1,2,3,4,5,6] and alloy [7,8,9] cathodes. Among them, silver has been found to possess extraordinary electrocatalytic properties toward the C-X (X = Cl, Br, I) bond cleavage for synthetic [10,11,12,13,14] and environmental [15,16,17,18,19] applications.…”

Section: Introductionmentioning

confidence: 99%

Gas-phase volatile organic chloride electroreduction: A versatile experimental setup for electrolytic dechlorination and voltammetric analysis

Lugaresi

Encontre

Locatelli

et al. 2014

Electrochemistry Communications

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Electroreduction of aliphatic chlorides at silver cathodes in water

Cited by 68 publications

References 48 publications

Disposal of Poisonous Organic Halides by Using the Electrochemical Method: DFT Simulation

Disposal of Poisonous Organic Halides by Using the Electrochemical Method: DFT Simulation

Rapid screening of silver nanoparticles for the catalytic degradation of chlorinated pollutants in water

Gas-phase volatile organic chloride electroreduction: A versatile experimental setup for electrolytic dechlorination and voltammetric analysis

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