Electrode Work Function and Absolute Potential Scale in Solid-State Electrochemistry

Tsiplakides, D.; Vayenas, C.G.

doi:10.1149/1.1362547

Cited by 111 publications

(88 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…formulated on the basis of (32), should be compared with exact Equation (21). Concluding, the "electron balances" formulated up to 1992 were slavishly related to the stoichiometric reaction notations.…”

Section: Mnomentioning

confidence: 99%

Formulation of Titration Curves for Some Redox Systems

Michałowska-Kaczmarczyk¹,

Rymanowski²,

Asuero³

et al. 2014

AJAC

View full text Add to dashboard Cite

show abstract

Section: Mnomentioning

confidence: 99%

Formulation of Titration Curves for Some Redox Systems

Michałowska-Kaczmarczyk¹,

Rymanowski²,

Asuero³

et al. 2014

AJAC

View full text Add to dashboard Cite

show abstract

“…By thoroughly examining the available literature, we first determine the most reliable experimental benchmark value for the ASHEP. Invoking the fundamental concepts of the absolute potential scale, developed by Trasatti and others, 1,[30][31][32][33][34][35] we then pinpoint the most appropriate choice for the reference level of the computed WF. Subsequently, by briefly revisiting our earlier works, we show how an internal ASHEP reference can be readily established.…”

Section: Introductionmentioning

confidence: 99%

Standard hydrogen electrode and potential of zero charge in density functional calculations

et al. 2011

View full text Add to dashboard Cite

Methods to explicitly account for half-cell electrode potentials have recently appeared within the framework of density functional theory. The potential of the electrode relative to the standard hydrogen electrode is typically determined by subtracting the experimental value of the absolute standard hydrogen electrode potential (ASHEP) from the calculated work function. Although conceptually correct, this procedure introduces two sources of errors: (i) the experimental estimate of the ASHEP varies from 4.28 to 4.85 V and, as has been previously shown and is reconfirmed here, (ii) the calculated work function strongly depends on the structure of the water film covering the metal surface. In this paper, we first identify the most accurate experimental reference for the ASHEP by revisiting up-to-date literature, and validate the choice of electron reference level in single-electrode density functional setups. By analyzing a dozen different water structures, built up from water hexamers, in their uncharged [potential of zero charge (PZC)] states on Pt(111), we then determine three different criteria (no net dipole, no charge transfer, and high water flexibility) that a water structure should possess in order for its computed ASHEP to closely match the experimental benchmark. We capture and quantify these three effects by calculating trends in the ASHEP and PZC on eight close-packed transition metals, considering the four most simple and representative water models. Finally, it is also demonstrated how the work function changes with exchange-correlation functional.

show abstract

“…102, products It has been shown that gold behaves as a good pseudoreference electrode, since previous NEMCA studies have shown a small variation of its potential (<0.1V) over the range of gaseous compositions used in the present study [15]. In all cases a series of blank experiments was carried out to confirm that the catalytic activity of the Au electrodes was negligible in comparison to that of the Rh catalyst.…”

Section: Productsmentioning

confidence: 63%

Electrochemical promotion of conventional and bipolar reactor configurations for NO reduction

Pliangos

Raptis

Bolzonella

et al. 2002

Ionics

Self Cite

View full text Add to dashboard Cite

Abstract. The reduction of NO by CO or C3H6 in the presence of 02, a reaction of great technological importance, was investigated on porous polycrystalline Rh catalyst films using a single-chamber and a wireless bipolar cell configuration. In the latter case the Rh catalyst films were deposited on the inner side of a YSZ tube, while two Au films deposited on the outer side of the tubes were used to polarize the Rh catalyst surface. The experimental conditions used in this study were close to those in the exhaust of a lean burn or diesel engine, i.e., high flowrates and space velocities and in some cases, considerable excess of oxygen. It was found that both direct (conventional) and indirect (wireless) polarization of the catalyst causes significant enhancement in the reaction rates (up to a factor of 20) and in the reactant conversion. These rate increases are strongly non-Faradaic with apparent Faradaic efficiencies, A, in the order of 100, manifesting the effect of Electrochemical Promotion or Non-faradaic Electrochemical Modification of Catalytic Activity (NEMCA).The Rh catalyst films were subsequently promoted in a classical way, via dry impregnation with NaOH, followed by drying and calcination. The thus Na-promoted Rh films were found to exhibit higher catalytic activity than the unpromoted films, with a considerable decrease in their light-off temperature. The effect of Electrochemical Promotion was then studied on these, already Na-promoted Rh catalysts. The results showed that the effect of Chemical and Electrochemical Promotion on the catalyst performance can be synergetic and their combination may lead to interesting practical applications. This is further supported by the fact that such bipolar tube configurations: (a) do not need electrical connection to the catalyst and (b) can be adapted easier to commercial exhaust units.

show abstract

Electrode Work Function and Absolute Potential Scale in Solid-State Electrochemistry

Cited by 111 publications

References 42 publications

Formulation of Titration Curves for Some Redox Systems

Formulation of Titration Curves for Some Redox Systems

Standard hydrogen electrode and potential of zero charge in density functional calculations

Electrochemical promotion of conventional and bipolar reactor configurations for NO reduction

Contact Info

Product

Resources

About