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Michalitsch, Richard; Laibinis, Paul E.

doi:10.1002/1521-3757(20010302)113:5<967::aid-ange967>3.3.co;2-c

Cited by 6 publications

(18 citation statements)

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“…In fact, Ag transitions at 352 eV (M 5 N 4,5 N 4,5 ) and 357 eV (M 4 N 4,5 N 4,5 ) are clearly observed, and accordingly, the intensity of the signal originated in the Au transitions at 70 eV (N 7 VV) decreases. The small Cl signal (180 eV, LMM) detected on the upd Ag can be assigned to an enhanced chloride anion adsorption on this surface . Again, the small oxygen and sulfur signals can be assigned to the sulfate anion adsorption on the Ag(1 × 1) monolayer deposited at upd …”

Section: Resultsmentioning

confidence: 87%

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Molecular Self-Assembly on Ultrathin Metallic Surfaces: Alkanethiolate Monolayers on Ag(1 × 1)−Au(111)

et al. 2004

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The self-assembly of alkanethiols on underpotentially deposited Ag(1 × 1)−Au(111) has been studied by using scanning tunneling microscopy, Auger electron spectroscopy, and electrochemical techniques. Even for short adsorbed alkanethiolates, the surface structure consists of an incommensurate hexagonal lattice with nearest-neighbor distances ≈ 0.48 nm that are usually found for long alkanethiolates adsorbed on the Ag(111) surface. Surprisingly, the stability of the self-assembled alkanethiolate monolayers against reductive electrodesorption is increased in ∼0.10 and 0.40 V with respect to those observed on Ag(111) and Au(111), respectively. Density-functional theory calculations for methanethiolate desorption from a model cluster indicate that the enhanced stability arises from a balance between the energy to introduce an electron into the alkanethiolate−Ag(1 × 1)−Au(111) system and the alkanethiolate desorption energy that is strongly modified by the Au substrate.

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Section: Resultsmentioning

confidence: 87%

“…The small Cl signal (180 eV, LMM) detected on the upd Ag can be assigned to an enhanced chloride anion adsorption on this surface. 38 Again, the small oxygen and sulfur signals can be assigned to the sulfate anion adsorption on the Ag(1 × 1) monolayer deposited at upd. 39 3.2.…”

Section: Preparation and Characterization Of The Ag(1 × 1)-au(111) Su...mentioning

confidence: 99%

Molecular Self-Assembly on Ultrathin Metallic Surfaces: Alkanethiolate Monolayers on Ag(1 × 1)−Au(111)

et al. 2004

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“…Defined as the electrodeposition of the monolayers or submonolayers of a foreign metal on a substrate at potentials that are more positive than the reversible or Nernst potential, UPD occurs when the adatom−substrate interaction is stronger than the adatom−adatom interaction. This phenomenon has been applied to catalysts, thin films, and sensors …”

Section: Introductionmentioning

confidence: 99%

Bimetallic Clusters by Underpotential Deposition on Layered Au Nanoparticle Films

et al. 2004

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In this paper, we describe the well-defined underpotential deposition systems consisting of Cu, Ag, Pb, and Tl on layered gold nanoparticle (AuNP) thin films linked with bifunctional 1,6-hexanedithiol (HDT). Scanning electron microscopy informs the morphological structures of layered AuNPs accumulated by stepwise immersion in citrate-stabilized AuNP and HDT solutions. Although cyclic voltammograms for typical Au oxide formation show that colloidal AuNP frameworks are polycrystalline, (111) reflection is the major character in X-ray diffraction measurements. As the AuNP layers are piled up on indium tin oxide, faradaic currents for the underpotential deposition adsorption increase linearly, indicating that entire AuNPs are electrochemically accessible; as a result, the mass transport and the electron transfer are plausible in AuNP frameworks. Voltammetric profiles of Ag on AuNP and Cu on AuNP exhibit similar features with those on the bulk metal film. On the other hand, heavy metal systems of Pb/AuNP and Tl/AuNP reveal more enhanced adsorption currents and particularly irreversible cyclic voltammograms which explicate their strong binding properties to AuNPs by the small size of the hydrated metal ions. This electrochemical approach gives an alternative route to the construction of bimetallic clusters. The potential cycling, X-ray photoelectron spectroscopy and scanning electron microscopy demonstrate that the bimetallic cluster of Ag or Cu on AuNPs is a coreshelled shape, while the bimetallic cluster of Pb or Tl on AuNPs forms an alloyed structure.

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“…Since the application of the scanning tunneling microscopy (STM) in an aqueous environment pioneered by Sonnenfeld and Hansma in 1986, electrochemists have possessed abilities to observe a surface process with real-space images at the electrified solid−liquid interface. Using these abilities, multifarious results were reported about the reconstruction of metal surfaces, , the adsorption on metal surfaces, , corrosion, , and growth phenomena of metals, which were all obtained under the potential control. , Among them, one of the most successful studies is the investigation of underpotential deposition (upd). , The research of upd systems triggers interests in fundamental as well as technical aspects such as catalysts, , thin-films, , sensors, and the modification of metal surfaces. , Among the numerous upd systems that have been characterized, silver upd on gold is one of the most widely studied. Gewirth et al reported the Ag upd on Au(111) by using in situ AFM, where the structure was dependent on the nature of the electrolyte.…”

Section: Introductionmentioning

confidence: 99%

Scanning Tunneling Microscopy Investigation of Silver Deposition upon Au(111) in the Presence of Chloride

Lee

Hwang

et al. 2002

Langmuir

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Using electrochemical measurements and in situ scanning tunneling microscopy (STM), we confirm the process of Ag growth and the overlayer structures of Ag underpotential deposition (upd) on Au(111) in the presence or absence of chloride anions. There are four distinct structures of the Ag adlayer on Au(111) in the presence of chloride. Adlayer structures (√3 × √3)R30°, (√19 × √19)R37°, (√13 × √13)R46°, and (6 × 6) are formed as a function of potential, and these structures are clearly matched to the features in a cyclic voltammogram. Compared with the (4 × 4) structure of Ag upd on Au(111) in a pure 0.1 M HClO4 solution, overlayer structures of Ag on Au(111) in a chloride-containing solution are more loosely packed. Therefore, we conclude that the structures of the Ag overlayer on Au(111) strongly interact with chloride anions, suggesting the bilayer structure is composed of both Ag and Cl.

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Cited by 6 publications

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Molecular Self-Assembly on Ultrathin Metallic Surfaces: Alkanethiolate Monolayers on Ag(1 × 1)−Au(111)

Molecular Self-Assembly on Ultrathin Metallic Surfaces: Alkanethiolate Monolayers on Ag(1 × 1)−Au(111)

Bimetallic Clusters by Underpotential Deposition on Layered Au Nanoparticle Films

Scanning Tunneling Microscopy Investigation of Silver Deposition upon Au(111) in the Presence of Chloride

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