The Electrochemistry of Oxygen

Hoare, James P.

doi:10.1149/1.2412261

Cited by 102 publications

(167 citation statements)

References 0 publications

Supporting

Mentioning

157

Contrasting

Unclassified

Order By: Relevance

“…1.36 V) reported much earlier for gold in acid by Vetter and Berndt (28) (this premonolayer oxidation feature at ca. 1.0 V was discussed later by Hoare (29) in terms of adsorbed oxygen). More dramatic, but still quite small, premonolayer oxidation responses were reported later for gold in base by Kirk and coworkers (30).…”

Section: The Electrochemistry Of Mms Goldmentioning

confidence: 93%

Scope for new applications for gold arising from the electrocatalytic behaviour of its metastable surface states

2004

View full text Add to dashboard Cite

The electrocatalytic behaviour of gold in aqueous media is surprisingly complex and a novel view of gold electrode surfaces is proposed to explain the observed electrochemical responses. The metal surface is considered as a chemically (or redox) modified electrode, with equilibrated, low energy, surface gold atoms functioning as a relatively inert support and low coverage, high energy, protruding gold atoms (or minute clusters of same) functioning as electrocatalytic redox mediators. The protruding atoms are viewed as surface active sites and the complex electrocatalytic behaviour is attributed to the basic instability of the mediators, the diversity (and poor control) of same, and the acid/base (or hydrolysis) behaviour of the oxidized states of the mediators. It is assumed that major advances in the application of gold in the heterogeneous catalysis of gas phase reactions will be accompanied by similar advances in the use of gold in the electrocatalysis area; however, this will require considerable work of both a practical and theoretical nature.

show abstract

Section: The Electrochemistry Of Mms Goldmentioning

confidence: 93%

Scope for new applications for gold arising from the electrocatalytic behaviour of its metastable surface states

2004

View full text Add to dashboard Cite

show abstract

“…However, owing to the extreme irreversibility of the oxygen evolution process, it has long been appreciated that the principle of microscopic reversibility is unlikely to apply to the oxygen electrode. 275 As a consequence, steady state kinetic data on the OER can only yield mechanistic information up to and including the rate-determining step (RDS). In the case of multistep reactions such as the OER the experimentally observed Tafel slope can be shown to be, [276][277][278][279][280] …”

Section: Kinetic Studies Of the Oermentioning

confidence: 99%

“…Over the years various possible mechanistic schemes have been proposed. Indeed, if all possible reaction intermediates are taken into account a large number of viable pathways for the OER can be envisaged, 297 although Hoare 275 and Kinoshita 298 both point out that by admitting a number of assumptions, the number of possible pathways can be reduced to ten or eleven. In Table 2 a summary of the diagnostic criteria for some of the most commonly considered oxygen evolution pathways is presented.…”

Section: Mechanistic Studies Of the Oermentioning

confidence: 99%

“…Thus, low Tafel slopes were attributed to the interaction of strongly adsorbed surface intermediates. 275,325 An alternative view point is highlighted in the mechanism of O'Grady 300 in Table 2, who emphasised the importance of oxide redox transitions in the course of the OER. In this often encountered concept, the OER is facilitated by the cyclic formation and decomposition of an unstable intermediate containing a metal centre in a higher valence state (z + 1) than its initial state (z).…”

Section: Mechanistic Studies Of the Oermentioning

confidence: 99%

See 1 more Smart Citation

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

Doyle

Godwin

Brandon

et al. 2013

Phys. Chem. Chem. Phys.

511

565

View full text Add to dashboard Cite

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.

show abstract

“…Thus, the open circuit potential (V oc ) of the cell is related to the activities of the reacting species (a i ) by the Nernst relationship [22,23] …”

Section: Resultsmentioning

confidence: 99%