Electrochemical catalysis in microemulsions. Dynamics and organic synthesis

Rusling, James F.; Zhou, De-Ling

doi:10.1016/s0022-0728(97)00374-4

Cited by 59 publications

(56 citation statements)

References 31 publications

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“…Recently, we demonstrated advantages of microemulsions (3) in selectivity or stereochemistry for several cyclization reactions using dissolved cobalt complex catalysts. If such reactions could be done using catalytic films attached to electrode surfaces (4), additional benefits including reusability, economy of catalyst, and improvements in efficiency might accrue (5)(6)(7).…”

Section: Introductionmentioning

confidence: 99%

Assembly of Electroactive Ordered Multilayer Films of Cobalt Phthalocyanine Tetrasulfonate and Polycations

Lvov

Kamau

Zhou

et al. 1999

Journal of Colloid and Interface Science

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Section: Introductionmentioning

confidence: 99%

Assembly of Electroactive Ordered Multilayer Films of Cobalt Phthalocyanine Tetrasulfonate and Polycations

Lvov

Kamau

Zhou

et al. 1999

Journal of Colloid and Interface Science

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Section: Introductionmentioning

confidence: 92%

“…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.…”

mentioning

confidence: 92%

“…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], fourDespite there being relevant experimental studies, theoretical studies of the dehalogenation have not been done for the organic polyhalides. Saveant [17] has developed a semi classical theory of concerted dissociative electron transfer based on the Morse curve approximation of the potential energy of the breaking bond and a Marcus-Hush solvent reorganization energy.…”

Section: Introductionmentioning

confidence: 99%

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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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“…Electrosynthesis in emulsion media (stabilized by the use of surfactants) has been pioneered by Rusling and coworkers [32][33][34]. The purpose of this article is to illustrate sonoelectrosynthetic processes in biphasic media via reference to three case studies, the electroreduction of liquid olefins, the Kolbe electrooxidation, and the electrogeneration of leuco-methylene green (all emulsions formed using 20 kHz power ultrasound).…”

Section: Introductionmentioning

confidence: 99%