The electrocatalytic oxidation of aliphatic alcohols in alkaline solutions at a nickel-based chemically modified glassy carbon electrode (Ni-CME) was investigated. The electrode was characterized by voltammetry and flow injection and applied for amperometric detection of mono- and polyhydric alcohols separated by liquid chromatography. A mechanistic electrooxidation model is proposed that involves a Langmuir-type adsorption process on different sites: NiO and NiOOH for polyhydric and monohydridic compounds, respectively. The process is followed by a hydrogen abstraction from the carbon a to the OH group through a radical pathway in the rate-determining step. Constantpotential amperometric detection was applied either after an anion-exchange chromatography with alkaline mobile phase or a size exclusion separation with a postcolumn addition of alkaline solution. Examples of applications, which include the separation and detection of simple alcohols present in real samples, are given.

Electrocatalytic Oxidation and Liquid Chromatographic Detection of Aliphatic Alcohols at a Nickel-Based Glassy Carbon Modified Electrode / I.G. Casella, T.R.I. Cataldi, A.M. Salvi, E. Desimoni. - In: ANALYTICAL CHEMISTRY. - ISSN 0003-2700. - 65:21(1993), pp. 3143-3150. [10.1021/ac00069a032]

Electrocatalytic Oxidation and Liquid Chromatographic Detection of Aliphatic Alcohols at a Nickel-Based Glassy Carbon Modified Electrode

E. Desimoni
Ultimo
1993

Abstract

The electrocatalytic oxidation of aliphatic alcohols in alkaline solutions at a nickel-based chemically modified glassy carbon electrode (Ni-CME) was investigated. The electrode was characterized by voltammetry and flow injection and applied for amperometric detection of mono- and polyhydric alcohols separated by liquid chromatography. A mechanistic electrooxidation model is proposed that involves a Langmuir-type adsorption process on different sites: NiO and NiOOH for polyhydric and monohydridic compounds, respectively. The process is followed by a hydrogen abstraction from the carbon a to the OH group through a radical pathway in the rate-determining step. Constantpotential amperometric detection was applied either after an anion-exchange chromatography with alkaline mobile phase or a size exclusion separation with a postcolumn addition of alkaline solution. Examples of applications, which include the separation and detection of simple alcohols present in real samples, are given.
Settore CHIM/01 - Chimica Analitica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/176430
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