Abstract
Rotating disk electrode system is mainly used to study the kinetics of reactions whose reactants have very low solubility in the electrolyte. For an irreversible reaction, Koutecky-Levich equation (K-L Eq.) is frequently used to deduce the kinetic current ik). Since K-L Eq. is derived based on the assumption that a system should conform the steady-state diffusion conditions, the data recoded from the actual system which deviates from such a condition, great error may be induced for the ik estimated. In this work, polarization curves for oxygen reduction reaction at polycrystalline Pt electrode recorded in solutions with various O2 concentrations and under various electrode rotation speeds have been analyzed systematically. Our analysis reveals that an error of 30% may be introduced by extrapolation to infinite rotation speed in solution with low O2 concentration or by including the data recorded under very slow electrode rotation speeds. The origins of the error and the ways to avoid such error are discussed.
Graphical Abstract
Keywords
gas electrode reaction, rotating disk electrode, Koutecky-Levich equation, diffusion, mmass transport, oxygen reduction reaction
Publication Date
2014-10-28
Online Available Date
2014-06-03
Revised Date
2014-05-27
Received Date
2014-01-15
Recommended Citation
Wei CHEN, Ling-wen LIAO, Zheng-da HE, Yan-xia CHEN.
On the Origin of the Errors of ik as Estimated from K-L Equation in Rotating Disk Electrode System[J]. Journal of Electrochemistry,
2014
,
20(5): 131167.
DOI: 10.13208/j.electrochem.131167
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol20/iss5/15
References
[1] Gottesfeld S. Electrocatalysis of oxygen reduction in polymer electrolyte fuel cells, a brief history and a critical examination of present theory and diagnostics[M]//, Koper M (Ed.), Fuel cell catalysis: A surface science approach. New Jersey: John Wiley & Sons, Inc., Hoboken, 2009: Chapter 9.
[2] Markovic N M, Schmidt T J, Stamenkovic V, et al. Oxygen reduction reaction on pt and pt bimetallic surfaces: A selective review[J]. Fuel Cells, 2001, 1(2): 105-116.
[3] Markovic N, Gasteiger H, Ross P N. Kineticsof oxygen reduction on Pt(hkl) electrodes: Implications for the crystallite size effect with supported Pt electrocatalysts[J]. Journal of The Electrochemical Society, 1997, 144(5): 1591-1597.
[4] Markovic N M, Gasteiger H A, Ross P N. Oxygen reduction on platinum low-index single crystal surfaces in sulfuric acid solution-rotating ring-Pt(HKL) disk studies[J]. Journal of Physical Chemistry, 1995, 99(11): 3411-3415.
[5] Zurilla R W, Sen R K, Yeager E. The Kinetics of the oxygen reduction reaction on gold in alkaline solution[J]. Journal of The Electrochemical Society, 1978, 125: 1103.
[6] Paulus U A, Schmidt T J, Gasteiger H A, et al. Oxygen reduction on a high-surface area Pt/Vulcan carbon catalyst: A thin-film rotating ring-disk electrode study[J]. Journal of Electroanalytical Chemistry, 2001, 495(2): 134-145.
[7] Schmidt T J, Paulus U A, Gasteiger H A, et al. The oxygen reduction reaction on a Pt/carbon fuel cell catalyst in the presence of chloride anions[J]. Journal of Electroanalytical Chemistry, 2001, 508(1/2): 41-47.
[8] Liao L W. Methodology and electrocatalysts for oxygen reduction reaction[D]. Hefei: University of Science and Technology of China, 2013.
[9] Masa J, Batchelor-McAuley C, Schuhmann W, et al. Koutecky-Levich analysis applied to nanoparticle modified rotating disk electrodes: Electrocatalysis or misinterpretation?[J]. Nano Research, 2014, 7(1): 71-78.
[10] van der Vliet D,Strmcnik D S,Wang C,et al. On the importance of correcting for the uncompensated ohmic resistance in model experiments of the oxygen reduction reaction[J]. Journal of Electroanalytical Chemistry, 2010, 647(1): 29-34.
[11] Bard A J, Faulkner L R. Electrochemical methods fundamentals and applicantions[M]. Chemical Industry Press(化学工业出版社), 2005: 230-245.
[12] Chen Y X,Li M F,Liao L W,et al. A thermostatic cell with gas diffusion electrode for oxygen reduction reaction under fuel cell relevant conditions[J]. Electrochemistry Communications, 2009, 11(7): 1434-1436.
[13] Yano H, Higuchi E, Uchida H, et al. Temperature dependence of oxygen reduction activity at Nafion-coated bulk Pt and Pt/carbon black catalysts[J]. Journal of Physical Chemistry B, 2006, 110(33): 16544-16549.
[14] Gasteiger H A, Kocha S S, Sompalli B, et al. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs[J]. Applied Catalysis B-Environmental, 2005, 56(1/2): 9-35.
[15] Chen D, Tao Q, Liao L W, et al. Determining the active surface area for various platinum electrodes[J]. Electrocatalysis, 2011, 2(3): 207-219.
[16] Liao L W(廖玲文), Chen D(陈栋), Chen Y X(陈艳霞), et al. Effect of catalyst loading on the evaluation of kinetic parameters of gas electrode reactions by using thin film rotating disk electrode method[J]. Scientia Sinica Chimica(中国科学). 2013, 43(2): 178-184.
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