Revealing structural effects: electrochemical reactions of butanols on platinum

Rodríguez, JL; Souto, RM; Fernández-Mérida, L; Pastor, E

HERO ID

1071394

Reference Type

Journal Article

Year

2002

Language

English

PMID

11981898

HERO ID 1071394
In Press No
Year 2002
Title Revealing structural effects: electrochemical reactions of butanols on platinum
Authors Rodríguez, JL; Souto, RM; Fernández-Mérida, L; Pastor, E
Journal Chemistry: A European Journal
Volume 8
Issue 9
Page Numbers 2134-2142
Abstract Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state.
Doi 10.1002/1521-3765(20020503)8:9<2134::AID-CHEM2134>3.0.CO;2-C
Pmid 11981898
Wosid WOS:000175511000018
Is Certified Translation No
Dupe Override No
Is Public Yes
Language Text English
Keyword adsorption; butanols; electrochemistry; mass spectrometry; platinum
Is Qa No