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Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
Published on: December 4, 2017
The kinetics of CO pathway in methanol oxidation at Pt electrodes, a quantitative study by ATR-FTIR spectroscopy
Shao Xiong Liu1, Ling Wen Liao, Qian Tao
1Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, China.
Abstract:
Methanol (MeOH) oxidation reaction (MOR) at Pt electrodes under potentiostatic conditions has been investigated by electrochemical in situ FTIR spectroscopy (FTIRS) in attenuated-total-reflection configuration under controlled flow conditions in 0.1 M HClO(4) 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 CO(ad) oxidation rate increases with the accumulation of CO(ad) until the maximum CO(ad) coverage (ca. 0.5 ML i.e., the steady state) is reached; (ii) at fixed CO(ad) coverage, the rates for MeOH decomposition to CO(ad) and CO(ad) oxidation 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 CO(ad) 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.
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