Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in baseThis article was submitted as part of a web theme on Future Electroanalytical Developments, highlighting important developments and novel applications. Also in this theme is work presented at the Eirelec 2011 meeting, dedicated to Professor Malcolm Smyth on the occasion of his 60th birthday.Electronic supplementary information (ESI) available. See DOI: 10.1039/c1cp22470k
Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling te...
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Language | English |
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29.11.2011
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Abstract | Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified
via
analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of
ca.
60 mV dec
−1
and
ca.
120 mV dec
−1
are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from
ca.
3/2 to
ca.
1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.
Hydrous iron oxyhydroxide films grown by potential cycling are effective electrocatalysts for the energetically demanding anodic oxygen evolution reaction. |
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AbstractList | Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified
via
analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of
ca.
60 mV dec
−1
and
ca.
120 mV dec
−1
are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from
ca.
3/2 to
ca.
1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.
Hydrous iron oxyhydroxide films grown by potential cycling are effective electrocatalysts for the energetically demanding anodic oxygen evolution reaction. |
Author | Lyons, Michael E. G Brandon, Michael P Doyle, Richard L |
AuthorAffiliation | Physical and Materials Electrochemistry Laboratory University of Dublin Trinity College School of Chemistry |
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Author_xml | – sequence: 1 givenname: Michael E. G surname: Lyons fullname: Lyons, Michael E. G – sequence: 2 givenname: Richard L surname: Doyle fullname: Doyle, Richard L – sequence: 3 givenname: Michael P surname: Brandon fullname: Brandon, Michael P |
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DOI | 10.1039/c1cp22470k |
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Notes | This article was submitted as part of a web theme on Future Electroanalytical Developments, highlighting important developments and novel applications. Also in this theme is work presented at the Eirelec 2011 meeting, dedicated to Professor Malcolm Smyth on the occasion of his 60th birthday. 10.1039/c1cp22470k Electronic supplementary information (ESI) available. See DOI |
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References_xml | – issn: 1956 end-page: p 337-341 publication-title: Magnetochemistry doi: Selwood – issn: 1982 end-page: p 209-223 publication-title: Proc. Symp. Electrocatalysis doi: O'Sullivan Burke – issn: 1969 end-page: p 369-483 publication-title: Mechanistic analysis of oxygen electrode reactions Modern Aspects of Electrochemistry doi: Damjanovic – issn: 2008 publication-title: Electrochemical Studies of the Oxygen Evolution Reaction at Passive Oxide Covered Ni, Co and Fe Electrodes in Aqueous Alkaline Solution doi: Brandon – issn: 2007 end-page: p 4-68 publication-title: CRC Handbook of Chemistry and Physics – issn: 1992 end-page: p 78-99 publication-title: Electrochemical Oxygen Technology doi: Kinoshita – issn: 1976 publication-title: Electroanal. Chem. doi: Woods – issn: 1990 end-page: 273 publication-title: Encyclopedia of Minerals – issn: 1964 end-page: 347 publication-title: Modern Aspects of Electrochemistry doi: Conway Gileadi – issn: 1965 end-page: 492 publication-title: Electrolyte Solutions doi: Robinson Stokes – issn: 1992 end-page: p1-48 publication-title: Molecular Design of Electrode Surfaces doi: Murray – issn: 1983 end-page: p 301-398 publication-title: Oxygen Electrochemistry Comprehensive Treatise of Electrochemistry doi: Tarasevich Sadkowski Yeager – issn: 2003 end-page: p 443-464 publication-title: Handbook of Fuel Cells-Fundamentals, Technology and Applications doi: Gattrell MacDougall – issn: 1978 end-page: 266 publication-title: Metal Ions in Solution doi: Burgess – issn: 2005 end-page: p 305-434 publication-title: Foundations of Colloid Science doi: Hunter – issn: 1992 publication-title: Electrochemical Oxygen Technology doi: Kinoshita – issn: 1981 publication-title: Adsorption of Inorganics at Solid-Liquid Interfaces doi: Schindler – issn: 1972 end-page: p 644-646 publication-title: Advanced Inorganic Chemistry doi: Cotton Wilkinson – issn: 1968 publication-title: The Electrochemistry of Oxygen doi: Hoare – issn: 1983 publication-title: The Electrochemical Behaviour of some Hydrous and Thermally Prepared Transition Metal Oxides doi: Lyons – issn: 1994 end-page: p 102-103 publication-title: Electroactive Polymer Electrochemistry doi: Lyons |
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Title | Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in baseThis article was submitted as part of a web theme on Future Electroanalytical Developments, highlighting important developments and novel applications. Also in this theme is work presented at the Eirelec 2011 meeting, dedicated to Professor Malcolm Smyth on the occasion of his 60th birthday.Electronic supplementary information (ESI) available. See DOI: 10.1039/c1cp22470k |
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