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Issue 43, 2013
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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)

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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−3 concentrations of model molecules containing (AAEM-relevant) cationic groups on the oxygen reduction reaction on a polycrystalline platinum disk (Ptpc) 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 O2 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 Ptpc 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.

Graphical abstract: 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)

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Publication details

The article was received on 06 Feb 2013, accepted on 20 Sep 2013 and first published on 23 Sep 2013


Article type: Paper
DOI: 10.1039/C3CP50556A
Citation: Phys. Chem. Chem. Phys., 2013,15, 18992-19000
  • Open access: Creative Commons BY license
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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)

    A. L. Ong, D. K. Whelligan, M. L. Fox and J. R. Varcoe, Phys. Chem. Chem. Phys., 2013, 15, 18992
    DOI: 10.1039/C3CP50556A

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