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http://dx.doi.org/10.5229/JKES.2005.8.3.117

Electrochemical Oxidation of Ethanol at Nickel Hydroxide Electrodes in Alkaline Media Studied by Electrochemical Impedance Spectroscopy  

Kim, Jae-Woo (Department of Chemistry and Center for Integrated Molecular Systems, Pohang University of Science and Technology)
Park, Su-Moon (Department of Chemistry and Center for Integrated Molecular Systems, Pohang University of Science and Technology)
Publication Information
Journal of the Korean Electrochemical Society / v.8, no.3, 2005 , pp. 117-124 More about this Journal
Abstract
Electrochemical oxidation of ethanol at nickel electrodes has been studied in 1 M KOH solution containing 0.20M ethanol using electrochemical impedance spectroscopy. Equivalent circuits have been worked out by simulating the impedance data, and the results were used to model the oxidation of ethanol as well as the passivation of the electrode. The maximum rate of oxidation of $Ni(OH)_2$ to NiOOH was observed at about 0.37V vs. Ag/AgCl reference electrode, while the maximum rate of ethanol oxidation at the Ni electrode was observed at about 0.42V, The charge-transfer resistance for oxidation of the electrode itself became smaller in the presence of ethanol than in its absence. These results suggest that the $\beta-Ni(OH)_2/\beta-NiOOH$ redox couple is acting as an effective electron transfer mediator far ethanol oxidation. The kinetic parameters also were obtained by the experimental and simulated results.
Keywords
Ethanol oxidatio; Nickel Hydroxide Electrode; Impedance;
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1 L. W. H. Leung, S. C. Chang, and M. J. Weaver, J. Electroanal. Chem., 266, 317 (1989)   DOI   ScienceOn
2 P. Gao, S. C. Chang, Z. Zhou, and M. J. Weaver, 'Electrooxidation pathways of simple alcohols at platinum in pure nonaqueous and concentrated aqueous environments as studied by real-time ftir spectroscopy', J. Electroanal. Chem., 272, 161 (1989)   DOI   ScienceOn
3 S.-M. Park, N. C. Chen, and N. Doddapaneni, 'Electrochemical oxidation of ethanol in aqueous carbonate solutions', J. Electrochem. Soc., 142, 40 (1995)   DOI   ScienceOn
4 J.-W. Kim and S.-M. Park, 'In-situ XANES studies of electrodeposited nickel oxide films with metal additives for the electro-oxidation of ethanol', J. Electrochem. Soc., 150, E560 (2003)   DOI   ScienceOn
5 K. P. Ta and J. Newman, 'Mass Transfer and Kinetic Phenomena at the Nickel Hydroxide Electrode', J. Electrochem. Soc., 145, 3860 (1998)   DOI   ScienceOn
6 S. Motupally, C. C. Streinz, and J. W. Weidner, J. Electrochem. Soc., 142, 1401 (1995)   DOI   ScienceOn
7 R. D. Armstrong, 'Impedance plane display for an electrode with diffusion restricted to a thin layer', J. Electroanal. Chem., 198, 177 (1986)   DOI   ScienceOn
8 M. F. Mathias and O. Haas, 'An alternating current impedance model including migration and redox-site interactions at polymer-modified electrodes', J. Phys. Chem., 96, 3174 (1992)   DOI
9 C. Y. Chao, L. F. Lin, and D. D. Macdonald, J. Electrochem. Soc., 129, 1874 (1982)   DOI   ScienceOn
10 G Vertes and G Horanyi, 'Some problems of the kinetics of the oxidation of organic compounds at oxide-covered nickel electrodes', J. Electroanal. Chem., 52, 47 (1974)   DOI   ScienceOn
11 G Barral, S. Maximovitch, and F. Njanjo-Eyoke, 'Study of electrochemically formed $Ni(OH)_2$ layers by EIS', Electrochim. Acta, 41, 1305 (1996)   DOI   ScienceOn
12 J.-W. Kim and S.-M. Park, 'Electrochemical Oxidation of Ethanol at Thermally Prepared $RuO_2$-Modified Electrodes in Alkaline Media', J. Electrochem. Soc., 146, 1075 (1999)   DOI   ScienceOn
13 S. Maximovitch, 'Influence of formation conditions on impedance properties of nickel passive layers formed in 1 M KOH', Electrochim. Acta, 41, 2761 (1996)   DOI   ScienceOn
14 C. Y. Chao, L. F. Lin, and D. D. Macdonald, J. Electrochem. Soc., 128, 1187 (1981)   DOI   ScienceOn
15 L. F. Lin, C. Y. Chao, and D. D. Macdonald, J. Electrochem. Soc., 128, 1194 (1981)   DOI   ScienceOn
16 B. A. Boukamp, Equivalent Circuit User 's Manual, 2nd ed., University of Twente, Enschede, the Netherlands (1989)
17 B. J. Johnson and S.-M. Park, 'Electrochemistry of Conductive Polymer XIX. Oxidation of Aniline at Bare and PolyanilineModified Platinum Electrodes Studied by Electrochemical Impedance Spectroscopy', J. Electrochem. Soc., 143, 1269 (1996)   DOI
18 M. Cai and S.-M. Park, 'Spectroelectrochemical studies on dissolution and passivation of zinc electrodes in alkaline solutions', J. Electrochem. Soc., 143, 2125 (1996)   DOI   ScienceOn
19 D. K. Cha and S.-M. Park, 'Electrochemical Oxidation of Mn(OH)2 in Alkaline Media', J. Electrochem. Soc., 144, 2573 (1997)   DOI   ScienceOn
20 S.-M. Park and J.-S. Yoo, 'Electrochemical impedance spectroscopy for better electrochemical measurements', Anal. Chem. 75, 455A (2003)
21 A. J. Bard and L. R. Faulkner, Electrochemical Methods, John Wiley & Sons, Inc. (1980)
22 P. W. T. Lu and S. Srinivasan, J. Electrochem. Soc., 125, 1416 (1978)   DOI   ScienceOn
23 Y. L. Lo and B. J. Hwang, J. Electrochem. Soc., 142,445 (1995)   DOI   ScienceOn
24 A. Gorenstein, F. Decker, W. Estrada, C. Esteves, A. Andersson, S. Passerini, S. Pantaloni, and B. Scrosati, 'Electrochromic NiOxHy, hydrated films: cyclic voltammetry and ac impedance spectroscopy in aqueous electrolyte', J. Electroanal. Chem., 277, 277 (1990)   DOI   ScienceOn
25 X. Qian, H. Sarnbe, D. E. Rarnaker, K. I. Pandya, and W. E. O'Grady, J. Phys. Chem., 101, 9441 (1997)   DOI   ScienceOn
26 S. H. Glarurn and J. H. Marshall, J. Electrochem. Soc., 129, 535 (1982)   DOI   ScienceOn
27 S. J. Lenhart, D. D. Macdonald, and B. G Pound, J. Electrochem. Soc., 135, 1063 (1988)   DOI   ScienceOn
28 S. D. Bhakta, D. D. Macdonald, B. G Pound, and M. Urquidi-Macdonald, J. Electrochem. Soc., 138, 1353 (1991)   DOI
29 D. D. Macdonald, M. Urquidi-Macdonald, S. D. Bhakta, and B. G Pound, J. Electrochem. Soc., 138, 1359 (1991)   DOI
30 M. A. Reid and P. L. Loyselle, 'Impedances of nickel electrodes cycled in various KOH concentrations', J. Power Sources, 36, 285 (1991)   DOI   ScienceOn
31 M. S. Suresh, 'Double-layer impedance of a nickel oxide electrode at low states-of-charge', J. Power Sources, 47, 27 (1994)   DOI   ScienceOn
32 M. Cappadonia, J. Divisek, T. von der Heyden, and U. Stimming, 'Oxygen evolution at nickel anodes in concentrated alkaline solution', Electrochim. Acta, 39, 1559 (1994)   DOI   ScienceOn
33 G Barral, F. Njanjo-Eyoke, and S. Maximovitch, 'Characterisation of the passive layer and of hydroxide deposits of nickel by impedance spectroscopy', Electrochim. Acta, 40, 2815 (1995)   DOI   ScienceOn
34 D. M. MacArthur, J. Electrochem. Soc., 117, 422 (1970)   DOI
35 V. Mancier, A. Metrot, and P. Willmann, 'Ac impedance modelling of nickel hydroxide electrodes viewed as mixed protonic-electronic conductors', Electrochim. Acta, 41, 1259 (1996)   DOI   ScienceOn
36 M. Fleischmann, K. Korinek, and D. Pletcher, J. Chem. Soc. Perkin II, 1396 (1972)
37 H. Bode, K. Delhmelt, and J. Whitte, 'Zur kenntnis der nickelhydroxidelektrode? I. Uber das nickel (Il)-hydroxidhydrat', Electrochim. Acta, 11, 1079 (1966)   DOI   ScienceOn
38 R. S. Schrebler Guzman, J. R. Vilche, and A. J. Arvia, J. Electrochem. Soc., 125, 1578 (1978)   DOI   ScienceOn
39 R. Barnard and C. F. Randell, J. Appl. Electrochem., 13, 89 (1983)   DOI   ScienceOn
40 R. Barnard and C. F. Randell, J. Appl. Electrochem., 13, 97 (1983)   DOI   ScienceOn
41 C. Zhang and S.-M. Park, 'The anodic oxidation of nickel in alkaline media studied by spectroelectrochemical techniques', J. Electrochem. Soc., 134, 2966 (1987)   DOI   ScienceOn
42 C. Zhang and S.-M. Park, 'In-situ spectroelectrochemical studies on the anodic oxidation of nickel hydroxide in alkaline media', J. Electrochem. Soc., 136, 3333 (1989)   DOI
43 J. McBreen, W. E. O'Grady, G Tourillon, E. Dartyge, A. Fontaine, and K. I. Pandya, 'In situ time-resolved x-ray absorption near edge structure study of the nickel oxide electrode', J. Phys. Chem., 93, 6308 (1989)   DOI
44 K. I. Pandya, W. E. O'Grady, D. A. Corrigan, J. McBreen, and R. W. Hoffinan, 'Extended x-ray absorption fine structure investigations of nickel hydroxides', J. Phys. Chem., 94, 21 (1990)   DOI
45 D. Guay, G. Tourillon, E. Dartyge, A. Fontaine, J. McBreen, K. I. Pandya, and W. E. O'Grady, 'In-situ time-resolved EXAFS study of the structural modifications occurring in nickel oxide electrodes between their fully oxidized and reduced states', J. Electroanal. Chem., 305, 83 (1991)   DOI   ScienceOn
46 K. I. Pandya, R. W. Hoffinan, J. McBreen, and W. E. O'Grady, J. Electrochem. Soc., 137, 383 (1990)   DOI