Electrochemical Oxidations of Several Organic Compounds in Aqueous Surfactant Suspensions Using Higher Valence Oxides as Intermediates

Abstract

Copper(II) oxide and manganese(II) oxide were shown to be catalysts for the electro-oxidation of 2-chloroethyl ethyl sulfide, diethylsulfide, 2-hydroxyethyl ethyl sulfide, and l-ehlorobutane in aqueous suspensions containing cationic surfactants. These oxides were shown to act as catalysts by formation of eopper(III), manganese(III), and manganese(IV) oxides which chemically oxidized the organic compounds. Analysis of the product suspensions showed the production of only the sulfoxide by oxidation of the 2-chloroethyl ethyl sulfide and diethyl sulfide. Destruction of chlorobutane was catalyzed by both barium peroxide and eopper(II) oxide. Volatile product(s) was trapped in a liquid nitrogen trap during electrolysis. These products included butane and butene.

Environmental Electrochemistry

“…PCBs and other organohalides have been dechlorinated in microemulsions [67][68][69], and organohalides have been preconcentrated and catalytically reduced at surfactantcoated electrodes [70][71][72][73]. Work has also been conducted (especially by T. Franklin et al) on the electrooxidation of a variety of organics including organosulfur and organohalide compounds in aqueous sufactant systems using oxidation catalysts such as barium peroxide, copper (2+) oxide, and bismuth (3+) oxide [74][75][76]. The higher oxidation state of the oxide drives the organic oxidation reaction and is regenerated in the lower oxidation state, ready for reuse.…”

Bismuth(III) and Copper(II) Oxides as Catalysts for the Electro‐Oxidation of Organic Compounds

“…Coulometric studies of the oxidation of the inorganic compounds led to the hypothesis that the intermediates formed in the oxidations were barium superoxide,4'5 copper(III), and manganese(III), and manganese(IV). 7 This is a report on a study of bismuth(III) oxide as an electro-oxidation catalyst. It was expected that bismuth(III) would be oxidized to bismuth(V), and it is known that bismuth(V) is a strong oxidizing agent.…”

“…As a suspended powder, it had already been shown that it could be oxidized to copper(III), and that this species could be used to electro-oxidize several organic compounds. 7 The first attempt to make a solid electrode that produced copper(III) was done with a copper wire electrode. A cationic surfactant was added to the electrolyte to increase the available potential range to a point where one could form copper(III); however, at potentials only slightly above 0.7 V the wire began to corrode, and this corrosion accelerated rapidly with increases in potential.…”

Estudos de adsorção em interfaces SnO2|H2O

“…Além dos íons H+ e OH-, os surfactantes constituem uma outra classe de adsorbatos que tem merecido extensos estudos para os sistemas óxido/solução. A adsorção de tensoativos nestes sistemas possibilita alterar as características hidrofilicas da superficie do óxido, o que sugere um vasto campo de investigação, de interesse nas áreas de eletrocatálise [8][9][10][11][12][13], processamento de materiais cerâmicos [14], fonnulação de pigmentos [15] e flotação de minérios [15,16]. Na área de eletrocatálise, a adsorção dos tensoativos pode ser utilizada para controlar a "arquitetura molecular" da interfase eletrodo Isolução, através da fOlmação de um revestimento que pode atuar nos processos de catálise, pré-concentração ou inibição de reações de transferência de carga, por exemplo [8].…”