The Electrochemistry of Iron in lM Lithium Hydroxide Solution at 22° and 200°C

Macdonald, Digby D.; Owen, Derrek G.

doi:10.1149/1.2403446

Cited by 104 publications

(53 citation statements)

References 27 publications

(91 reference statements)

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“…For a polycrystalline Fe electrode polished to a ''mirror bright'' finish, we usually observed four well-defined anodic peaks (A1-A4) and two cathodic peaks (C1, C2) during the initial stages of oxidation, reflecting surface redox processes involving bound oxy iron species. This fine structure has been observed by other workers, [14][15][16][17][18][19][20][21][22][23][24] and the general features of the voltammetric response remain unchanged, even if the concentration of base is increased. The various features have been previously assigned, both by us, 12 and other workers.…”

Section: Cyclic Voltammetry Measurementssupporting

confidence: 80%

Redox switching and oxygen evolution electrocatalysis in polymeric iron oxyhydroxide films

Lyons

Brandon

2009

Phys. Chem. Chem. Phys.

101

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Outstanding issues regarding the redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been examined. Charge percolation through the hydrous layer has been quantified, using cyclic voltammetry, in terms of a charge transport diffusion coefficient D CT which admits a value of ca. 3 Â 10 À10 cm 2 s À1 . Steady-state Tafel plot analysis and electrochemical impedance spectroscopy have been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec À1 and ca. 120 mV dec À1 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.

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Section: Cyclic Voltammetry Measurementssupporting

confidence: 80%

Redox switching and oxygen evolution electrocatalysis in polymeric iron oxyhydroxide films

Lyons

Brandon

2009

Phys. Chem. Chem. Phys.

101

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“…The present interpretation is supported by the fact that peak 2 is correlated by the cathodic peak 2', which has to be associated with the reduction of a bulk oxide back to metallic iron as also supported by other kinetic dataa8), 9), 19) Moreover, the present data do not indicate any correlation between the magnitude or potential of the peak and the previous history of hydrogen evolution on the surface. Peak 2 is preceded by at least two oxidation processes that cause significant structural changes at the surface.…”

Section: Resultssupporting

confidence: 88%

“…Macdonald and Owen19) have argued that further oxidation of Fe(OH)2 into magnetite is, at least in part, responsible for this peak. However, later interpretations ter view is based largely on the apparent conjugation of peaks 3 and 2' on pure iron8), 9), 19).…”

Section: Resultsmentioning

confidence: 99%

“…Since peak 4 splits into two maxima, two successive processes take part, and the first of these (peak 4a) corresponds to selective dissolution of aluminum as discussed earlier. The fact that the peak becomes larger at each consecutive sweep indicates that parallel oxidation processes, probably those responsible for the anodic peak 3, are also in progress7) 19). A fraction of the charge transferred must be due to the oxidation of fresh metallic iron formed as a result of aluminum dissolution.…”

Section: Peakmentioning

confidence: 99%

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Electrochemical behavior of Al3Fe intermetallic compound.

Nisancioḡl̄ū¹

1993

Journal of Japan Institute of Light Metals

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The cathodic processes localized to iron rich intermetallic phases on commercial aluminum alloys during corrosion in neutral chloride environments are controlled by the structural and compositional changes occurring on these phases in a locally stable alkaline environment. These phenomena are investigated by conventional electrochemical techniques on synthetically grown Al3Fe crystals. The surface of the crystals is enriched by metallic iron at E<-1.175 VscE as a result of selective aluminum dissolution. In the potential range -1.175

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“…84 These various features, reflecting surface redox processes involving surface bound oxy iron species, have been assigned by a number of authors in the literature. [186][187][188][189][190][191][192][193][194][195] Our current viewpoint is primarily informed by the work of Burke and Lyons. 84 Peak A1 is most probably due to the formation of a layer of adsorbed hydroxy species,…”

Section: Interfacial Redox Chemistry Of Iron Based Electrodes In Alkamentioning

confidence: 99%

Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes

Doyle

Godwin

Brandon

et al. 2013

Phys. Chem. Chem. Phys.

521

565

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This paper presents a review of the redox and electrocatalytic properties of transition metal oxide electrodes, paying particular attention to the oxygen evolution reaction. Metal oxide materials may be prepared using a variety of methods, resulting in a diverse range of redox and electrocatalytic properties. Here we describe the most common synthetic routes and the important factors relevant to their preparation. The redox and electrocatalytic properties of the resulting oxide layers are ascribed to the presence of extended networks of hydrated surface bound oxymetal complexes termed surfaquo groups. This interpretation presents a possible unifying concept in water oxidation catalysis -bridging the fields of heterogeneous electrocatalysis and homogeneous molecular catalysis. In contextOver the past 50 years considerable research efforts have been devoted to the realisation of efficient, economical and renewable energy sources. Metal oxide materials have played a large part in this drive with demonstrated applications at both the research and commercial level. Their use in areas such as batteries, fuel cells and water electrolysis has resulted in the development of materials with a diverse range of structural and chemical properties. In all cases, understanding the fundamental electrochemistry of the material can be invaluable for rational design and optimisation. This review focuses on the redox, charge transport and electrocatalytic properties of transition metal oxide electrodes as they pertain to the electrolytic splitting of water. Particular emphasis is placed on the nature of the active surface which is interpreted in terms of hydrated interlinked oxymetal complexes termed surfaquo groups. In this way, the review seeks to bridge the gap between heterogeneous electrocatalysis and homogeneous molecular catalysis for water oxidation, areas of considerable modern interest and activity.

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The Electrochemistry of Iron in lM Lithium Hydroxide Solution at 22° and 200°C

Cited by 104 publications

References 27 publications

Redox switching and oxygen evolution electrocatalysis in polymeric iron oxyhydroxide films

Redox switching and oxygen evolution electrocatalysis in polymeric iron oxyhydroxide films

Electrochemical behavior of Al3Fe intermetallic compound.

Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes

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