Reconstruction phenomena at metal-electrolyte interfaces

Kolb, Dieter M.

doi:10.1016/0079-6816(96)00002-0

Cited by 567 publications

(667 citation statements)

References 91 publications

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“…78,79 In such configuration, both the STM substrate and tip are fully controlled by the electrochemical potential versus a common reference electrode. Using in situ STM, reconstruction of metallic electrode surfaces at the solid/liquid interfaces under electrochemical potential control, 80 metal deposition, [81][82][83] anion adsorption 25,84,85 and organic molecule adsorption 82 have been characterized at atomic or/and molecular level. In situ STM has even been employed for nanofabrication of metallic nanoclusters or pits with precise positioning and designed patterns on the well defined surfaces.…”

Section: In Situ Scanning Tunnelling Microscopymentioning

confidence: 99%

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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Self-assembled organization of functional molecules on solid surfaces has developed into a powerful and sophisticated tool for surface chemistry and nanotechnology. A number of reviews on the topic have been available since the mid 1990s. This perspective article aims to focus on recent development in the investigations of electronic structures and assembling dynamics of electrochemically controlled self-assembled monolayers (SAMs) of thiol containing molecules on gold surfaces. A brief introduction is first given and particularly illustrated by a Table summarizing the molecules studied, the surface lattice structures and the experimental operating conditions. This is followed by discussion of two major high-resolution experimental methods, scanning tunnelling microscopy (STM) and single-crystal electrochemistry. In Section 3, we briefly address choice of supporting electrolytes and substrate surfaces, and their effects on the SAM structures. Section 4 constitutes the major body of the article by offering some details of recent studies for the selected cases, including in situ monitoring of assembling dynamics, molecular electronic structures, and the key external factors determining the SAM packing. In Section 5, we give examples of what can be offered by theoretical computations for the detailed understanding of the SAM electronic structures revealed by STM images. A brief summary of the current applications of SAMs in wiring metalloproteins, design and fabrication of sensors, and single-molecule electronics is described in Section 6. In the final two sections (7 and 8), we discuss the current status in understanding of electronic structures and properties of SAMs in electrochemical environments and what could be expected for future perspectives.

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Section: In Situ Scanning Tunnelling Microscopymentioning

confidence: 99%

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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“…In addition to the Au islands resulting from the lifting of Au(111) reconstruction, 14 clusters containing porphyrin adsorbates can be resolved, as 1.55 nm wide aquares.…”

Section: Potential-dependent Adsorption-desorption Processes Of Tpyp mentioning

confidence: 99%

Adsorption and Electrochemical Activity: An In Situ Electrochemical Scanning Tunneling Microscopy Study of Electrode Reactions and Potential-Induced Adsorption of Porphyrins

Borguet

2006

J. Phys. Chem. B

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The effect of adsorption on molecular properties and reactivity is a central topic in interfacial physical chemistry. At electrochemical interfaces, adsorbed molecules may lose their electrochemical activity. The absence of in situ probes has hindered our understanding of this phenomenon and electrode reactions in general. In this work, classical electrochemistry and electrochemical scanning tunneling microscopy (EC-STM) were combined to provide molecular level insight into electrochemical reactions and the molecular adsorption state at the electrolyte-electrode interface. The metal-free porphyrin 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) adsorbed on Au(111) in 0.1 M H 2 SO 4 solution was chosen as a model system. TPyP is found to irreversibly adsorb on Au(111) over a wide range of potentials, from -0.25 to 0.6 V SCE . The adsorption state of TPyP has a dramatic effect on its electrochemistry. Preadsorbed, oxidized TPyP displays no well-defined cathodic peaks in cyclic voltammograms in sharp contrast to solution-phase TPyP. Our present work provides direct, molecular level evidence of the electrochemically "invisible" species. Electrochemical activity of absorbed species is recovered by allowing the oxidized molecule sufficient time (tens of minutes) to reduce. The redox state of adsorbed TPyP also affects the nature of the adsorption. Oxidized species can apparently only form monolayers. However, multilayers, stable enough to be imaged by STM, can form when the adsorbed TPyP is in the reduced state. This suggests that by controlling the electrochemistry one can either promote or suppress the formation of multilayers.

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“…This phenomenon provides an explanation for the diverse kinetics reported previously for the phase transition. 9 Under metastable conditions, small islands decay while islands greater than a critical size, determined here to be 100 nm 2 , frequently grow before ultimately decaying, providing evidence for electrochemical Ostwald ripening in this system.…”

Section: Introductionmentioning

confidence: 99%

“…Au(111) has two stable phases: the unreconstructed (1 × 1) and the reconstructed (22 × 3). 9 At room temperature, the (22 × 3) phase is stable, while the first-order phase transition to the (1 × 1) phase requires heating to 880 K under ultrahigh vacuum (UHV). 10 In an electrochemical environment, however, the phase transition can be induced by changing the electrode potential.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of Metastable Nanoscale Island Growth and Dissolution at Electrochemical Interfaces by Time-Resolved Scanning Tunneling Microscopy

and

Borguet

2001

J. Phys. Chem. B

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The dynamics of nanoscale island growth, stability, and dissolution, accompanying the potential-induced phase transitions between the (22 × 3) and (1 × 1) structures of the Au(111) surface in 0.1 M HClO 4 solution, have been investigated by potential pulse perturbation time-resolved scanning tunneling microscopy (P 3 TR-STM). Starting from a potential at which the reconstructed (22 × 3) phase is stable, a short positive potential pulse briefly brings the electrode to a potential at which the (1 × 1) phase is stable. This pulse induces a perturbation that lifts the Au(111)-(22 × 3) reconstruction completely, resulting in nanoscale island formation on the surface. The nanoscale islands are metastable and dissolve with time. The initial average island area and the island decay rate are related to the pulse amplitude and duration. The higher and longer the pulse, the smaller the average size of the islands produced and the more slowly the islands decay. This result reveals a "voltammetric annealing" process that may be important in stable island formation at electrochemical interfaces. The dynamics of individual islands are quite heterogeneous and nonmonotonic. Small islands decay faster than large islands. Even under metastable conditions, large islands frequently grow before ultimately decaying, providing evidence for electrochemical Ostwald ripening in this system. A simple model, based on perimeter detachment as the rate-limiting step, provides a qualitative explanation for the observed decay dynamics.

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Reconstruction phenomena at metal-electrolyte interfaces

Cited by 567 publications

References 91 publications

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Adsorption and Electrochemical Activity: An In Situ Electrochemical Scanning Tunneling Microscopy Study of Electrode Reactions and Potential-Induced Adsorption of Porphyrins

Dynamics of Metastable Nanoscale Island Growth and Dissolution at Electrochemical Interfaces by Time-Resolved Scanning Tunneling Microscopy

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