Determination of the potential of zero charge of Au(1 1 1) electrodes modified with thiol self-assembled monolayers using a potential-controlled sessile drop method

Iwami, Yasunobu; Hobara, Daisuke; Yamamoto, Masahiro; Kakiuchi, Takashi

doi:10.1016/j.jelechem.2003.11.028

Cited by 37 publications

(65 citation statements)

References 38 publications

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“…Thus, shifting the potential from +0.3 V to À0.1 V is expected to bring the LD-MHA/electrolyte interface closer to the PZC and thereby increase the solid/liquid interfacial tension (approach the electrocapillary maximum), in accordance with the well-known Lippmann equation [45]. If the observed change in wettability of the film is linked to this change in excess surface charge density at the electrode, then Young's equation predicts that the contact angle of the film should increase upon approaching the PZC (with increasing solid/liquid interfacial tension) [46]. However, the fact that we observe a decrease in the contact angle of the LD-MHA SAM upon shifting the potential from +0.3 V to À0.1 V indicates that the change in wettability of the SAM is not the result of voltage-induced changes in the excess surface charge density on the electrode.…”

Section: Evidence Of Conformational Change Within Ld-mha Samssupporting

confidence: 66%

Factors governing the reversible change in ionic permeability of a low-density monolayer

Olivier

Shin

Fréchette

2010

Journal of Electroanalytical Chemistry

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Section: Evidence Of Conformational Change Within Ld-mha Samssupporting

confidence: 66%

Factors governing the reversible change in ionic permeability of a low-density monolayer

Olivier

Shin

Fréchette

2010

Journal of Electroanalytical Chemistry

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“…For a value of E pzc,θ=1 , a good estimate is −0.49 V (vs. Ag|AgCl|satd. KCl), which was obtained from the potential-dependent contact angle measurements of a UT SAM on Au(111) [103], and agrees with an earlier estimate reported using a Wilhelmy method, −0.5 V (vs. SCE) for a dodecanethiol SAM [104].…”

Section: Contribution Of Charging Currentsupporting

confidence: 90%

Voltammetry of the Reductive Desorption of Thiol Self‐assembled Monolayers from Electrode Surface

Kakiuchi

2007

Encyclopedia of Electrochemistry

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The voltammetry of the reduction desorption of organothiolate molecules in a self-assembled monolayer on a metal surface, first reported by Porter and his coworkers [1,2], has been widely used for diagnosing the adsorbed state of the self-assembled monolayer (SAM) and for nanometer-scale engineering of SAMs [55][56][57][58][59][60][61][62][63][64][65]. When the electrode covered with a single-component SAM of a thiol derivative is cathodically polarized, typically in an aqueous alkaline solution, a single peak or more complicated multiple peaks appear on the voltammogram. The shape and the location of the peak can be utilized for studying the surface properties of the SAMs. The reductive desorption in an alkaline medium is formally written aswhere RS-M and RS − represent the organothiolate adsorbed on the metal surface and the organothiolate in the solution after the desorption. The actual mechanism of the desorption is, however, more complicated than what is expressed in Eq.(1), as the desorption is a cooperative process where the adsorbed thiolate molecules are tightly packed in a regular array, for example, the ( (111). The shape of the voltammogram is strongly affected by the state of the monolayer, such as the packing density and the magnitude of the lateral interaction between the adsorbed molecules. This means that the electrochemical signal reflects the state of the monolayer; the shape of the voltammogram contains rich information regarding not only the molecular properties of adsorbed thiolates but also those related to the state of the monolayer. Another electrochemical technique employed is chronoamperometry, which usually shows the nucleation and growthtype transients in the timescale of less than a few tenths of a second, depending on the type of desorbing thiolates [7,31,[66][67][68][69], and is therefore suitable for studying the kinetics of desorption. In this chapter, the first part summarizes the fundamental properties of the voltammetry of the reductive desorption of SAMs. The second part introduces a model of the reductive desorption that can account for the salient features of the voltammetry of the reductive desorption. The third part deals with the voltammetry of binary SAMs and its use for studying and engineering the SAMs. 7.5.1 Voltammetry of the Reductive Desorption of SAMs: Experimental Features Reductive Desorption of Alkanethiolate SAMsThe shape of the voltammograms for the desorption of alkanethiolate SAMs depends on the state of the monolayer. Figure 1 shows cyclic voltammograms recorded in 0.5 mol dm −3 aqueous KOH for the Au(111) electrodes after being immersed in a 1 µmol dm −3 ethanol solution of undecanethiol (UT) for different periods of time. Two humps at −0.6 V and −1 V seen at short immersion times metamorphoses into a single peak at −1.05 V. This change in the shape of the voltammograms reflects the change of the adsorbed state of the UT molecules, which though initially lying flat on the surface, gradually stand Encyclopedia of Electrochemistry. Edited by A.J. Bard and...

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“…On the other hand, the double-layer capacitances between the SAM-modified electrodes and the electrolyte solution are created in the electrochemical environment. The potential of zero charge (pzc) of n-alkanethiol SAMs is known to be about −1.5 V vs Au/AuO x [46,47]. Thus, both the tip and sample electrodes are positively charged, as schematically shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Force Curve Measurements between n-Decanethiol Self-Assembled Monolayers in Inert Solvent and in Electrochemical Environment

Yokota

Yamada

Kawai

2009

e-J. Surf. Sci. Nanotechnol.

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It was revealed that electrostatic forces between electrodes under the applied bias are almost completely suppressed by an electrochemical potential control. The force operating between n-decanethiol self-assembled monolayers (SAMs) on gold was examined by atomic force microscopy in liquid n-dodecane and in an aqueous solution of HClO4. In inert n-dodecane, the bias voltage was simply applied between the tip and the sample, and the force curve exhibited a long-range attractive force in accordance with the simple capacitance model. Meanwhile under the independent control of the tip and sample potentials in HClO4, the force curve did not depend on the applied potentials due to the small double-layer capacitance.

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Determination of the potential of zero charge of Au(1 1 1) electrodes modified with thiol self-assembled monolayers using a potential-controlled sessile drop method

Cited by 37 publications

References 38 publications

Factors governing the reversible change in ionic permeability of a low-density monolayer

Factors governing the reversible change in ionic permeability of a low-density monolayer

Voltammetry of the Reductive Desorption of Thiol Self‐assembled Monolayers from Electrode Surface

Force Curve Measurements between n-Decanethiol Self-Assembled Monolayers in Inert Solvent and in Electrochemical Environment

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