Continuous work function monitoring for electrode emersion

Rath, D.L.; Kolb, Dieter M.

doi:10.1016/0039-6028(81)90432-5

Cited by 94 publications

(40 citation statements)

References 6 publications

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“…Experiments of hydrophobic emersion using resistance and work function monitoring have shown the existence and stability of an emersed double layer and have confirmed that the surface can be removed from solution with the double layer intact 20,21 Both XPS and ERS (External Reflection Spectroscopy) have been able to monitor the structure and composition of the double layer 22,23 and have shown that the emersed double layer is similar or identical to the double layer in solution, that little or no discharge of the double layer occurs upon emersion and that the structure and orientation of molecules in the double layer are undisturbed by transfer to a UHV. 24 However, certain precautions must be taken to ensure a 'good' emersion from solution.…”

Section: Introductionmentioning

confidence: 79%

Structural changes during oxidation of Au(110)

Hale

Thurgate

Wilkie

2001

Surface & Interface Analysis

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The gold(110) single crystal exhibits a (1 × 2) surface structure when clean, but when immersed in 0.01 M HClO 4 under potential control the structure has been found to change. Throughout the double-layer region the structure remains as .1 × 2/ but when the potential is increased above 0.9-1.0 V vs. Ag/AgCl (the preoxidation region) the surface structure changes to a centred rectangular structure. This structure forms reproducibly but has limited stability. After the initial oxidation, the structure prevails until 1.2-1.3 V, whereupon oxidation occurs on a larger scale and the surface structure becomes .1 × 1/. These structures return to .1 × 2/ after reduction of the oxide, proving that the structural changes are reversible. X-ray photoelectron spectroscopy of these regions has shown a difference in the chemical state of the oxygen. Adsorbed perchlorate ion is initially the only oxygen component but as the potential increases the peak shifts into the hydroxide region and finally splits into a hydroxide peak and a metal oxide peak. This study indicates a new way of looking at the structure and composition of the gold surface and provides insight into the nature of the interaction between the surface and the solution.

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Section: Introductionmentioning

confidence: 79%

Structural changes during oxidation of Au(110)

Hale

Thurgate

Wilkie

2001

Surface & Interface Analysis

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“…Furthermore, Kelvin probe measurements on emersed electrodes have indicated that the double-layer structure developed by applied potential during immersion is maintained for short times when the sample is removed from solution. 32,33 The linear relation between the open-circuit potential and Volta potential is interesting given that the environments are different. For instance, some of the metals studied, such as Fe and Cu, might have a surface film in air that is very different than that in solution.…”

Section: Resultsmentioning

confidence: 99%

Characterization of AA2024‐T3 by Scanning Kelvin Probe Force Microscopy

Schmutz

Frankel

1998

J. Electrochem. Soc.

420

364

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Volta potential mapping of AA2024-T3 on surfaces was performed with an atomic force microscope. A linear relation was found between the Volta potential measured in air and the corrosion potential in aqueous solution for a range of pure metal samples, indicating that this potential is a measurement of the practical nobility of the surface. Large differences in the Volta potential of intermetallic particles in AA2024-T3 and the matrix phase resulted in a potential map with high contrast that clearly identifies the location of the particles. All intermetallic particles, including the Mg-containing S-phase particles, had a Volta potential noble to that of the matrix. Surface films on the particles and the matrix were found to have strong effects on the potential, and probably explain the noble nature of the Mg-containing particles, which have been reported to be active to the matrix in solution. The effect of these surface films was examined by refreshing the sample surface using different techniques. Lateral heterogeneities in certain intermetallic particles were also revealed.

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“…Despite all this pioneering work, some uncertainties still exist on the exact value of the absolute standard hydrogen potential (the IUPAC recommended value is 4.44 V [14] but some of the published emersed electrode work [9,11,12,17,18] had suggested somehow higher values, closer to 4.7 V).…”

Section: Introductionmentioning

confidence: 97%

“…The underlying concepts are not complex, but sometimes elusive, and the experimental difficulties, at least in aqueous electrochemistry, rather significant, so that it took the work of several prominent scientists, including Bockris and co-workers [1,2], Frumkin and Damaskin [3,4], Gileadi et al [1], Kanevsky [5], Reiss and Heller [6], Parsons [7], Gomer and Tryson [8], Hansen and Hansen [9], Gerischer and Ekardt [10], Kolb and Rath [11,12] and Trasatti [13][14][15][16] to define, clarify and quantify the absolute potential concept. Despite all this pioneering work, some uncertainties still exist on the exact value of the absolute standard hydrogen potential (the IUPAC recommended value is 4.44 V [14] but some of the published emersed electrode work [9,11,12,17,18] had suggested somehow higher values, closer to 4.7 V).…”

Section: Introductionmentioning

confidence: 99%

Absolute potential measurements in solid and aqueous electrochemistry using two Kelvin probes and their implications for the electrochemical promotion of catalysis

2007

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The concept of absolute electrode potential in aqueous and solid electrochemistry is discussed in light of the first experimental investigation utilizing a two Kelvin probe system which allows for direct in situ measurement of the work functions of both the, emersed or spillover modified, working and reference electrodes.In both cases, i.e. emersed electrodes in aqueous electrochemistry and spillover-modified electrodes in solid electrochemistry, it is found that the following two equations relate the working-reference electrode potential difference, U WR , and the work functions, U W and U R of the emersed or spillover-modified working and reference electrodes:where U WR is varied either by varying the gaseous composition or via a potentiostat. These equations show that the work function of emersed electrodes in aqueous electrochemistry or of spillover-modified electrodes in solid state electrochemistry is the natural choice of the absolute electrode potential:The value U 0 H2 ðabsÞ ¼ 4:46 AE 0:15 V was obtained as the absolute potential value of the H 2 /H + electrode in aqueous solutions at p H2 ¼1 bar, pH = 0 and T = 298 K, while the value of U 0 O2 ðabsÞ ¼ 5:14 AE 0:05 V was measured as the absolute potential value of the O 2 /O 2) electrode in YSZ (8 mol% Y 2 O 3 -stabilized-ZrO 2 ) at p O2 ¼ 1 bar and T = 673 K.

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Continuous work function monitoring for electrode emersion

Cited by 94 publications

References 6 publications

Structural changes during oxidation of Au(110)

Structural changes during oxidation of Au(110)

Characterization of AA2024‐T3 by Scanning Kelvin Probe Force Microscopy

Absolute potential measurements in solid and aqueous electrochemistry using two Kelvin probes and their implications for the electrochemical promotion of catalysis

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