Electrocatalysis at polycrystalline silver in base: an example of the complexity of surface active state behaviour

Ahern, Andrea J.; Nagle, Lorraine C.; Burke, Declan

doi:10.1007/s10008-001-0263-2

Cited by 25 publications

(17 citation statements)

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“…The dashed lines in Fig. 5 show that despite the major difference in the surface states involved the oxide formation peak potentials in (a) coincide rather well with the onset potentials for electrocatalytic reduction in (b); evidently the same basic types of active state transitions are involved at both interfaces (similar correlations were discussed recently for silver (37) …”

Section: Some Electrochemical Correlationssupporting

confidence: 78%

“…the high coverage gold MMS states formed on reduction decay rapidly. However, if a gold surface is superactivated by a combination of thermal and cathodic pretreatment, under milder conditions than used when producing the CBE, a total of five well defined anodic peaks may be observed within the double layer region, see However, it is assumed that such active state transitions occur in a quasi-reversible manner at low coverage active sites; this view is supported by the results of Kirk and coworkers (30) and data for the behaviour of silver in base (37). In summary, MMS gold electrochemistry is quite novel and still in an exploratory stage.…”

Section: The Electrochemistry Of Mms Goldmentioning

confidence: 86%

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

2004

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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.

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Section: Some Electrochemical Correlationssupporting

confidence: 78%

Section: The Electrochemistry Of Mms Goldmentioning

confidence: 86%

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

2004

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“…It has long been known that the activity of electrodes (and of heterogeneous catalysts) is associated with surface defects [1][2][3][4][5][6][7][8][9]; platinum black is a familiar example [10]. In contrast, deactivation is typically achieved by "brute-force" methods such as total passivation [11,12].…”

Section: Introduction and Resultsmentioning

confidence: 99%

Selective Knockout of Gold Active Sites

et al. 2010

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KEYWORDS Electrochemistry • gold • kinetics • radicals • voltammetry 2 ABSTRACTIt has long been known that defects on a gold surface play an important role in electrocatalysis, but the precise mechanism has always been unclear. This work indicates that the defect sites provide partially filled d-orbitals that stabilize freeradical intermediates. Strong evidence for this hypothesis is that the sites can be selectively knocked out by treatment with OH• radicals generated by Fenton's reagent. The knockout effect is demonstrated using oxygen reduction, hydrogen reduction, and the redox electrochemistry of hydroquinone.

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“…to demonstrate that surface metastability (which entails the presence of surface defects) plays a vital role in the electrodeposition, electrocatalytic and bath additive behaviour in the case of copper in acid solution. The background to Metastable Metal Surface (MMS) states [16] and their role in electrocatalysis was discussed recently for the Gp 11 metals (Au, Ag and Cu) [17][18][19] and RuO 2 [20]; earlier work on the electrocatalytic properties of copper in base [21,22], is also worth noting. The essential point is that solid metal surfaces possess two limiting states, designated EMS and MMS (EMS = Equilibrated Metal Surface).…”

Section: Introductionmentioning

confidence: 98%

Involvement of a metastable surface state in the electrocatalytic, electrodeposition and bath additive behaviour of copper in acid solution

et al. 2006

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Copper in aqueous sulphuric acid solution at room temperature displays a low level active (metastable) surface state redox transition well within the double layer region, at ca. )0.7±0.1 V (SMSE). The latter is an important feature of this electrode system as it apparently coincides with (a) the transition from activation to transport control in acid sulphate copper plating baths, (b) a major change in the inhibiting properties of several plating bath additives, and (c) the onset/termination potential of electrocatalytic processes, e.g. nitrate reduction, at copper in acid. The nature and influence of this active surface state behaviour, which is assumed to be relevant to Damascene copper plating, is discussed.

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Electrocatalysis at polycrystalline silver in base: an example of the complexity of surface active state behaviour

Cited by 25 publications

References 0 publications

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

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

Selective Knockout of Gold Active Sites

Involvement of a metastable surface state in the electrocatalytic, electrodeposition and bath additive behaviour of copper in acid solution

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