Share This Article:

Enhanced Electrocatalytic Reduction of Oxygen at Electrodes Coated with a Multi-Metallic Co(II)/Pt(II) Porphyrin

Abstract Full-Text HTML XML Download Download as PDF (Size:977KB) PP. 54-59
DOI: 10.4236/ajac.2013.410A1007    3,255 Downloads   4,857 Views   Citations

ABSTRACT

Edge plane pyrolytic graphite (EPG) electrodes coated with the Co(II)/Pt(II)2 analog of 5,15-bis-(4-pyridyl)-10,20-bis-(3-methoxy-4-hydroxyphenyl)porphyrin undergo an electrochemical-chemical-electrochemical (ECE) reaction when anodically scanned in 1.0 M sulfuric acid. The new redox couple formed from this anodic conditioning of the coated electrode is dependent on the pH of the solution. Roughened EPG electrodes coated with the Co(II)/Pt(II)2 trimetallic porphyrin show a catalytic shift of 400 mV for the reduction of O2 when compared to the reduction of O2 at a bare EPG electrode. An additional catalytic shift of ca. 150 mV is observed for O2 reduction at an EPG electrode coated with the Co(II)/Pt(II)2 porphyrin which has been oxidized in 1.0 M sulfuric acid. In addition to the added electrocatalysis, a significant percentage of O2 reduced at the oxidized Co(II)/Pt(II)2 EPG electrode is converted to H2O as determined by rotating disk electrode measurements.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

S. Swavey and D. Fresh, "Enhanced Electrocatalytic Reduction of Oxygen at Electrodes Coated with a Multi-Metallic Co(II)/Pt(II) Porphyrin," American Journal of Analytical Chemistry, Vol. 4 No. 10A, 2013, pp. 54-59. doi: 10.4236/ajac.2013.410A1007.

References

[1] G. Farmer and D. J. Hamblin, “First on the Moon,” Little, Brown, and Co., 1970.
[2] S. Wasmus and A. Küver, “Methanol Oxidation and Direct Methanol Fuel Cells: A Selective Review,” Journal of Electroanalytical Chemistry, Vol. 461, No. 1-2, 1999, pp. 14-31.
[3] H. Jahnke, M. Schonborn and G. Zimmermann, “Organic Dyestuffs as Catalysts for Fuel Cells,” Topics in Current Chemistry, Vol. 61, 1976, pp. 133-181.
http://dx.doi.org/10.1007/BFb0046059
[4] Y. Kiros, “Metal Porphyrins for Oxygen Reduction in PEMFC,” International Journal of Electrochemical Science, Vol. 2, 2007, pp. 285-300.
[5] J. E. Newton and M. B. Hall, “Generalized Molecular Orbital Calculations on Transition-Metal Dioxygen Complexes: Models for Iron and Cobalt Porphyrins,” Inorganic Chemistry, Vol. 23, No. 26, 1984, pp. 4627-4632.
http://dx.doi.org/10.1021/ic00194a043
[6] C. Shi, B. Steiger, M. Yuasa and F. C. Anson, “Electroreduction of O2 to H2O at Unusually Positive Potentials Catalyzed by the Simplest of the Cobalt Porphyrins,” Inorganic Chemistry, Vol. 36, No. 20, 1997, pp. 4294-4295.
http://dx.doi.org/10.1021/ic970516s
[7] E. Song, C. Shi and F. C. Anson, “Comparison of the Behavior of Several Cobalt Porphyrins as Electrocatalysts for the Reduction of O2 at Graphite Electrodes,” Langmuir, Vol. 14, No. 15, 1998, pp. 4315-4321.
http://dx.doi.org/10.1021/la980084d
[8] C. Shi and F. C. Anson, “Multiple Intramolecular Electron Transfer in the Catalysis of the Reduction of Dioxygen by Cobalt meso-Tetrakis(4-pyridyl)porphyrin to Which Four Ru(NH3)5 Groups are Coordinated,” Journal of the American Chemical Society, Vol. 113, No. 25, 1991, pp. 9564-9570. http://dx.doi.org/10.1021/ja00025a022
[9] C. Shi and F. C. Anson, “Electrocatalysis of the Reduction of O2 to H2O by Tetraruthenated Cobalt mesoTetrakis(4-pyridyl)porphyrin Adsorbed on Graphite Electrodes,” Inorganic Chemistry, Vol. 31, No. 24, 1992, pp. 5078-5083. http://dx.doi.org/10.1021/ic00050a029
[10] B. Steiger, C. Shi and F. C. Anson, “Electrocatalysis of the Reduction of Dioxygen by Adsorbed Cobalt 5,10,15, 20-Tetraarylporphyrins to Which One, Two, or Three Ru (NH3)52+ Centers are Coordinated,” Inorganic Chemistry, Vol. 32, No. 10, 1993, pp. 2107-2113.
http://dx.doi.org/10.1021/ic00062a038
[11] C. Shi and F. C. Anson, “Comparison of the Catalytic Reduction of Dioxygen by [5,10,15, 20-tetrakis((pentaamineruthenium(II))4-pyridyl)porphyrinato]cobalt(II) in Solution and on Graphite Electrode Surfaces,” Inorganic Chemistry, Vol. 34, No. 18, 1995, pp. 4554-4561.
http://dx.doi.org/10.1021/ic00122a010
[12] C. Shi and F. C. Anson, “Cobalt meso-Tetrakis(N-methyl-4-pyridiniumyl)porphyrin Becomes a Catalyst for the Electroreduction of O2 by Four Electrons When [(NH3)5Os]n+ (n = 2,3) Groups are Coordinated to the Porphyrin Ring,” Inorganic Chemistry, Vol. 35, No. 26, 1996, pp. 7928-7931. http://dx.doi.org/10.1021/ic9607189
[13] F. C. Anson, C. Shi and B. Steiger, “Novel Multinuclear Catalysts for the Electroreduction of Dioxygen Directly to Water,” Accounts of Chemical Research, Vol. 30, No. 11, 1997, pp. 437-444. http://dx.doi.org/10.1021/ar960264j
[14] K. Araki and H. E. Toma, “Synthesis and Electrochemical Behavior of a Tetrametallated Cobalt Porphyrin,” Inorganica Chimica Acta, Vol. 179, No. 2, 1991, pp. 293-296.
[15] T. Malinski, A. Ciszewski, J. Bennet, J. R. Fish and L. Czuchajowski, “Characterization of Conductive Polymeric Nickel(II) Tetrakis(3-methoxy-4-hydroxyphenyl) Porphyrin as an Anodic Material for Electrocatalysis,” Journal of The Electrochemical Society, Vol. 138, No. 7, 1991, pp. 2008-2015. http://dx.doi.org/10.1149/1.2085915
[16] T. Malinski and Z. Taha, “Nitric Oxide Release from a Single Cell Measured in situ by a Porphyrinic-Based Microsensor,” Nature, Vol. 358, 1992, pp. 676-677.
http://dx.doi.org/10.1038/358676a0
[17] T. Malinski, A. Ciszewski, J. Fish, E. Kubaszewski and L. Czuchajowski, “Concuctive Polymeric Cu(II) Tetrakis (3-methoxy-4-hydroxyphenyl) Porphyrin as a Photosensitizer in a Photoelectrochemical Cell,” Advanced Materials, Vol. 4, No. 5, 1992, pp. 354-357.
http://dx.doi.org/10.1002/adma.19920040508
[18] X. Wu, Y. Li, B. Grundig, N.-T. Yu and R. Rennenberg, “A Novel Iron-Porphyrin Derived Oxygen Sensor Working Near 0 V (vs. Ag/AgCl) in Neutral Solution,” Electroanalysis, Vol. 9, No. 16, 1997, pp. 1288-1290.
http://dx.doi.org/10.1002/elan.1140091614
[19] G. Richards and S. Swavey, “Electrooxidation of Fe, Co, Ni, and Co Metalloporphyrins on Edge-Plane Pyrolytic Graphite Electrodes and Their Electrocatalytic Ability towards the Reduction of Molecular Oxygen in Acidic Media,” European Journal of Inorganic Chemistry, Vol. 2009, No. 35, 2009, pp. 5367-5376.
http://dx.doi.org/10.1002/ejic.200900651
[20] K. Gadamsetti and S. Swavey, “Electrocatalytic Reduction of Oxygen at Electrodes Coated with a Bimetallic Cobalt(II)/Platinum(II) Porphyrin,” Dalton Transactions, No. 46, 2006, pp. 5530-5535.
[21] J. H. Price, A. N. Williamson, R. F. Schramm and B. B. Wayland, “Palladium(II) and Platinum(II) Alkyl Sulfoxide Complexes. Examples of Sulfur-Bonded, Mixed Sulfur and Oxygen-Bonded, and Totally Oxygen-Bonded Complexes,” Inorganic Chemistry, Vol. 11, No. 6, 1972, pp. 1280-1284. http://dx.doi.org/10.1021/ic50112a025
[22] F. Pariente, E. Lorenzo and H. D. Abruna, “Electrocatalysis of NADH Oxidation with Electropolymerized Films of 3,4-Dihydroxybenzaldehyde,” Analytical Chemistry, Vol. 66, No. 23, 1994, pp. 4337-4344.
http://dx.doi.org/10.1021/ac00095a034

  
comments powered by Disqus

Copyright © 2019 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.