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Issue 20, 2011
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The kinetics of CO pathway in methanol oxidation at Pt electrodes, a quantitative study by ATR-FTIR spectroscopy

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Abstract

Methanol (MeOH) oxidation reaction (MOR) at Pt electrodes under potentiostatic conditions has been investigated by electrochemical in situFTIR spectroscopy (FTIRS) in attenuated-total-reflection configuration under controlled flow conditions in 0.1 M HClO4 with 2 M MeOH, where the mass transport effects are largely eliminated using a flow cell. Our results reveal that (i) at constant potentials, the methanol dehydrogenation rate decreases while the COadoxidation rate increases with the accumulation of COad until the maximum COad coverage (ca. 0.5 ML i.e., the steady state) is reached; (ii) at fixed COad coverage, the rates for MeOH decomposition to COad and COadoxidation increases with potential from 0.3 to 0.7 V (vs. RHE), with Tafel slopes for MeOH dehydrogenation of ca. 440 ± 30 mV/dec, which is independent of COad coverage; (iii) the current efficiency of the CO pathway in MOR at 0.6 and 0.7 V is below 20% and it decreases toward higher potentials. The mechanisms as well as the potential induced change in the kinetics of different pathways involved in MOR are briefly discussed.

Graphical abstract: The kinetics of CO pathway in methanol oxidation at Pt electrodes, a quantitative study by ATR-FTIR spectroscopy

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Publication details

The article was received on 06 Sep 2010, accepted on 18 Mar 2011 and first published on 18 Apr 2011


Article type: Paper
DOI: 10.1039/C0CP01728K
Citation: Phys. Chem. Chem. Phys., 2011,13, 9725-9735
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    The kinetics of CO pathway in methanol oxidation at Pt electrodes, a quantitative study by ATR-FTIR spectroscopy

    S. X. Liu, L. W. Liao, Q. Tao, Y. X. Chen and S. Ye, Phys. Chem. Chem. Phys., 2011, 13, 9725
    DOI: 10.1039/C0CP01728K

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