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Impact of 1 mmol dm(-3) concentrations of small molecules containing nitrogen-based cationic groups on the oxygen reduction reaction on polycrystalline platinum in aqueous KOH (1 mol dm(-3))

Ong, AL, Whelligan, Daniel, Fox, ML and Varcoe, John (2013) Impact of 1 mmol dm(-3) concentrations of small molecules containing nitrogen-based cationic groups on the oxygen reduction reaction on polycrystalline platinum in aqueous KOH (1 mol dm(-3)) PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 15 (43). pp. 18992-19000.

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Abstract

Alkaline anion-exchange membranes (AAEMs) containing cationic head-groups (e.g. involving quaternary ammonium and imidazolium groups) are of interest with regard to application in alkaline polymer electrolyte fuel cells (APEFCs). This initial ex situ study evaluated the effect of 1 mmol dm concentrations of model molecules containing (AAEM-relevant) cationic groups on the oxygen reduction reaction on a polycrystalline platinum disk (Pt) electrode in aqueous KOH (1 mol dm(-3)). The cationic molecules studied were tetramethylammonium (TMA), benzyltrimethylammonium (BTMA), 1-benzyl-3-methylimidazolium (BMI), 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane (BAABCO) and 6-(benzyloxy)-N,N,N-trimethylhexan-1-aminium (BOTMHA). Both cyclic and hydrodynamic linear sweep rotating disk electrode voltammetry techniques were used. The resulting voltammograms, derived estimates of apparent electrochemically active surface areas, Tafel slopes, apparent exchange-current densities and the number of electrons transferred (per O molecule) were compared. The results strongly suggest that 1 mmol dm(-3) concentrations of BTMA, BAABCO, and (especially) BMI seriously inhibit the catalytic activities of Pt in an aqueous KOH electrolyte at 25 °C. The negative influence of (benzene-ring-free) TMA and Cl anions (KCl control experiment) appeared to be less severe. The separation of the trimethylammonium group from the benzene ring via a hexyloxy spacer chain (in BOTMHA) also produced a milder negative effect.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Ong, ALUNSPECIFIEDUNSPECIFIED
Whelligan, DanielD.Whelligan@surrey.ac.ukUNSPECIFIED
Fox, MLUNSPECIFIEDUNSPECIFIED
Varcoe, JohnJ.Varcoe@surrey.ac.ukUNSPECIFIED
Date : 23 September 2013
Identification Number : 10.1039/c3cp50556a
Copyright Disclaimer : © the Owner Societies 2013
Uncontrolled Keywords : Science & Technology, Physical Sciences, Chemistry, Physical, Physics, Atomic, Molecular & Chemical, Chemistry, Physics, ANION-EXCHANGE MEMBRANES, ELECTROLYTE FUEL-CELLS, ALKALINE-MEDIUM, HEAD-GROUPS, POLYMER, OXIDATION, CATALYSTS, DEGRADATION, PERFORMANCE, NANOWIRES
Related URLs :
Additional Information : This is an Open Access article, licensed under a Creative Commons Attribution 3.0 Unported Licence.
Depositing User : Symplectic Elements
Date Deposited : 14 Mar 2014 18:22
Last Modified : 14 Jul 2017 08:46
URI: http://epubs.surrey.ac.uk/id/eprint/804722

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