1997
DOI: 10.1021/la970820y
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Modeling Electrochemical Interfaces in Ultrahigh Vacuum:  Influence of Progressive Cation and Surface Solvation upon Charge−Potential Double-Layer Behavior on Pt(111)

Abstract: Measurements of the work-function changes, ΔΦ, on Pt(111) for continuously increasing solvent exposures θs* and in the presence of various coverages of potassium, θK, in ultrahigh vacuum (UHV) at 90 K are reported with the objective of ascertaining how the surface charge−potential properties of such “UHV electrochemical model” interfaces are altered by progressive solvation. The solventswater, methanol, acetonitrile, acetone, and ammoniaspan a range of dipolar and other solvating properties and have been uti… Show more

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Cited by 20 publications
(8 citation statements)
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“…The desorption temperature of the water molecules in the high temperature peak increases along the sequence Cs, K, Na from 175 to 210 K. This implies that water molecules are stabilized by an attractive interaction with the alkalis, an effect which was observed previously on various metal substrates. [24][25][26][27][28] Our TDS studies indicate that the alkali-water interaction is larger for the lighter alkali following the increase of local charge density. We will show in this contribution that the stronger water-alkali interaction for lighter alkalis is linked to a faster stabilization dynamics.…”
Section: Experimental Details and Sample Characterizationmentioning
confidence: 68%
“…The desorption temperature of the water molecules in the high temperature peak increases along the sequence Cs, K, Na from 175 to 210 K. This implies that water molecules are stabilized by an attractive interaction with the alkalis, an effect which was observed previously on various metal substrates. [24][25][26][27][28] Our TDS studies indicate that the alkali-water interaction is larger for the lighter alkali following the increase of local charge density. We will show in this contribution that the stronger water-alkali interaction for lighter alkalis is linked to a faster stabilization dynamics.…”
Section: Experimental Details and Sample Characterizationmentioning
confidence: 68%
“…However, these measurements have shown displacement charges of about 60 μC/cm Pt 2 for Pt/BC and 20 μC/cm Pt 2 for Pt/C, respectively, in the double layer region (potentials of about 0.3 to 0.6 V vs. RHE) where chemisorbed hydrogen is unlikely to occur. Estimates for the pzc of extended Pt electrodes vary, but usually range from close to 0 V vs. SHE 12 to values closer to 0.25 V vs. SHE 13 . Regardless, Pt electrodes in the electrolyte used (0.1 M HClO 4 ) are typically reported to have a capacitance of around 15 μF/cm Pt 2 11-13 , which would suggest surface charges no larger than 10 μC/cm Pt 2 in the double layer region for unsupported Pt electrodes.…”
Section: Pt Nanoparticle Outer Surface Chargementioning
confidence: 99%
“…A field well-prepared to be the second step is experimental modeling of electrochemical interface in vacuum systems [201][202][203][204] (see also Section 4 in Ref. 205).…”
Section: Realistic and Visionary Dreamsmentioning
confidence: 99%
“…Finally, a strong advantage of vacuum experiments is their already formed stable link with real electrochemical phenomena, constructed in the 1990s by Weaver. [201][202][203] The data on work functions are available for platinized platinum as well, 206,207 so some feedback with classical data for this electrode material is possible. Current attempts to model the potential of zero charge for platinum/solution interface 208,209 can be probably linked in more natural manner just to experiments done in vacuum.…”
Section: Realistic and Visionary Dreamsmentioning
confidence: 99%