Underpotential deposition and electrocrystallization of metals: an in situ scanning tunnelling microscopy study with lateral atomic resolution

Obretenov, W.; Schmidt, Ute; Lorenz, W.J.; Staikov, G.; Budevski, E.; Carnal, D.; Müller, Ulrich; Siegenthaler, H.; Schmidt, Eberhard

doi:10.1039/fd9929400107

Cited by 29 publications

(15 citation statements)

References 18 publications

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“…Since CH 3 COO - is expected to be more strongly adsorbed than ClO 4 - , the absence of the A 1 /C 1 and A 3 /C 3 waves in CH 3 COO - solutions has been associated with blocking of the step edges by CH 3 COO - anions. In-situ STM imaging of the Ag(111) surface during upd of Pb supports this hypothesis. , The fact that we observe a more ideal voltammetric response and greatly diminished A 1 /C 1 and A 3 /C 3 waves in ClO 4 - solutions, while also observing a very broad wave in CH 3 COO - solutions, suggests that the nucleation and growth of a Pb upd layer may be accelerated by surface defect structures. This conclusion is supported by the observation that while the voltammetric wave shape in ClO 4 - solutions is rather insensitive to the scan rate, the voltammetric response in CH 3 COO - becomes more irreversible as the scan rate is increased.…”

Section: Resultssupporting

confidence: 72%

“…The initial investigations of Pb upd at Ag(111) by Bewick and Thomas suggested that the above voltammetric response corresponds to the deposition of ∼1 monolayer of Pb. , More recent in-situ grazing incidence X-ray diffraction (GIXS) measurements have demonstrated that the completed Pb upd layer is a closed-packed structure, rotated from the Ag(111) surface by ∼4.5°. − This structure has been recently confirmed by in-situ STM , for the same solution conditions and will be assumed in the discussion below.…”

Section: Resultsmentioning

confidence: 83%

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Influence of Surface Defect Structure on the Underpotential Deposition of Pb Monolayers at Ag(111)

1996

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The underpotential deposition (upd) of Pb monolayers at Ag(111) thin-film electrodes in perchlorate solutions have been investigated as a function of the substrate defect structure. Ag(111) films were grown epitaxially on muscovite mica by thermal evaporation and annealed at 300°C at 10 -6 Torr for periods between 0 and 12 h. X-ray diffraction and electrochemical scanning tunneling microscopy indicate that thermal annealing significantly increases the degree of film crystallinity and smoothness. A more ideal voltammetric response for the upd of Pb was obtained using Ag thin-film electrodes that were annealed for periods longer than 6 h. Specifically, the width of the upd voltammetric wave, as well as the splitting between the cathodic and anodic peaks, was found to decrease with an increase in annealing time. Surface roughness factors (defined as the ratio of the electrochemically-active area relative to the geometric area) for the Ag(111) films decreased from 1.15 for unannealed films to 0.99 ( 0.03 for films after 12 h of annealing. The results indicate that previously reported voltammetric features observed for the upd of Pb monolayers in perchlorate solutions are associated with Pb deposition at Ag(111) surface defect sites.

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Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 83%

Influence of Surface Defect Structure on the Underpotential Deposition of Pb Monolayers at Ag(111)

1996

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“…Much work has attended studies of Pb upd on Ag surfaces. STM work on Ag(111) [144][145][146] demonstrated that the full monolayer in this system also gave rise to a (1×1) monolayer which, like its counterpart on Au(111) also formed a moire ´pattern. Detailed analysis on this pattern allowed the authors to discern the degree of rotation (ca.…”

Section: Silver Surfacesmentioning

confidence: 86%

Electrochemical Applications ofin SituScanning Probe Microscopy

1997

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“…By far, the most studied UPD system on silver single crystals has been lead deposition. This process has been studied by a wide variety of techniques including electrochemical, ,− optical reflectivity, SHG, STM, ,,− X-ray absorption spectroscopy, X-ray scattering, − and UHV techniques such as low-energy electron diffraction and Auger electron spectroscopy. ,, Theoretical models of lead deposition on silver single crystals have also been proposed and studied. − …”

Section: Upd On Silver Surfacesmentioning

confidence: 99%

Underpotential Deposition at Single Crystal Surfaces of Au, Pt, Ag and Other Materials

2001

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Enrique Herrero was born in Salamanca, Spain, in 1967. He received his B.S. in Chemistry from the University of Alicante (Spain) in 1990. His graduate thesis dealt with the oxidation of methanol, formic acid, and CO on platinum single crystals and was completed in 1995 at the University of Alicante under the direction of Prof. Juan M. Feliu. During this time he spent one year working with Prof. Andrzej Wieckowski at the University of Illinois at Urbana-Champaign. In 1996 he went on to a postdoctoral appointment in the group of Prof. He ´ctor D. Abrun ˜a in the Chemistry Department at Cornell University, where he worked on metal deposition on single crystals. He is currently an assistant professor at the University of Alicante. Lisa Buller received a B.S. in Chemistry from the University of WisconsinsMadison in 1992. She obtained a Ph.D. in Chemistry from Cornell University in 1997 under the direction of Prof. H. D. Abrun ˜a. Her thesis work dealt with electrochemical and X-ray studies of metal deposition onto single crystals. She is currently an assistant professor at the University of WisconsinsPlatteville.

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Underpotential deposition and electrocrystallization of metals: an in situ scanning tunnelling microscopy study with lateral atomic resolution

Cited by 29 publications

References 18 publications

Influence of Surface Defect Structure on the Underpotential Deposition of Pb Monolayers at Ag(111)

Influence of Surface Defect Structure on the Underpotential Deposition of Pb Monolayers at Ag(111)

Electrochemical Applications ofin SituScanning Probe Microscopy

Underpotential Deposition at Single Crystal Surfaces of Au, Pt, Ag and Other Materials

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