Underpotential Deposition and Stripping of Lead at Disorganized Monolayer‐Modified Gold Electrodes

Herzog, Grégoire; Arrigan, Damien W. M.

doi:10.1002/elan.200503318

Cited by 13 publications

(7 citation statements)

References 26 publications

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“…We interpret the behaviour observed for the variation of M/n observed using EQCM with incorporation of side reactions into the deposition of Pb. Most of the mechanisms proposed for the formation of lead UPD is based on the reaction [25,26]:…”

Section: Resultsmentioning

confidence: 99%

On the electrodeposition mechanism of Pb on copper substrate from a perchlorate solution studied by electrochemical quartz crystal microbalance

Nasirpouri

2011

Ionics

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Electrodeposition mechanism of lead on polycrystalline copper from a perchlorate solution in the presence of chloride ions was investigated. Electrochemical quartz crystal microbalance data including frequency and resistance were simultaneously recorded with cyclic voltammograms and current transients. The change of frequency and resistance shows that a rigid bulk film forms at the potentials more negative than −0.52 V saturated calomel electrode (SCE), exhibiting the overpotential deposits of Pb (OPD). However, at the potentials ranging from −0.38 to −0.43 V SCE, a monolayer of lead as the underpotential deposit of Pb (UPD) is formed. The measured real mass of the OPD of Pb compared to the charge passed through the cell elucidates the formation of Pb (II). The magnitude of the applied overpotential has considerable effect on the growth of the OPD of lead. The Pb OPDs formed at the lower overpotentials (or applied potentials in a range of −0.54 to −0.58 V SCE) show slight positive deviation of the electrochemical equivalent (M/n) of Pb (II). We ascribe this evidence to the possible incorporation of adsorbed/ alloyed elements like chlorine in the film composition. At the higher overpotentials (or applied potentials of negative than −0.58 V SCE), the ratio starts to decrease, mainly due to the hydrogen evolution associated with the possible morphology change of deposit. Our results also show that the nucleation and growth of Pb OPD can be described with the instantaneous mechanism based on Scharifker-Hills prediction with nondimensional plots.

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Section: Resultsmentioning

confidence: 99%

On the electrodeposition mechanism of Pb on copper substrate from a perchlorate solution studied by electrochemical quartz crystal microbalance

Nasirpouri

2011

Ionics

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“…silver) electrode 5,9 . As the graphite solid composite electrodes do not contain any mercury, they present (as well as metallic composite 1,5,8,[10][11][12][13][14]32 , metallic 26,33,34 , solid amalgam and solid composite amalgam electrodes 9,35-39 ) an acceptable electrode material in all analytical laboratories.…”

Section: Discussionmentioning

confidence: 98%

“…A selected group of metals (Pb, Cd, Cu, Tl and Bi) was studied and their interactions on the electrode surface were described in detail. This paper is focused on studies realized using a CCE, while most of the paper on this topic so far published have been devoted to the study of the UPD effect and its analytical applications on solid monocrystalline or polycrystalline electrodes (e.g refs [21][22][23][24][25][26][27] ) on screenprinted electrodes 28 or on metal-plated rotograved carbon electrodes 29 , i.e. on purely metallic materials (Au, Ag).…”

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confidence: 99%

Anodic stripping voltammetry using graphite composite solid electrode

Navrátil

Barek

Kopanica

2009

Collect. Czech. Chem. Commun.

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Dedicated to the memory of Professor Jaroslav Heyrovský on the occasion of the 50th anniversary of the Nobel Prize for polarography.A graphite (carbon) composite solid electrode, prepared from graphite powder and epoxy resin, was used as a working electrode for anodic stripping voltammetry. The underpotential deposition effect, which appears at metallic electrodes, was clearly observed on this type of electrode as well. In the case of a simultaneous deposition of two metals on the surface of the composite solid electrode, the anodic dissolution of the metal, which is anodically dissolved at more negative potentials, is substantially influenced by the presence of the other deposited metal. This effect was exploited for the determination of lead in the presence of other metals by differential pulse anodic stripping voltammetry. The article presents possible applicability of such a type of very simple composite electrode to studies of the underpotential deposition effect as well as for analytical purposes.

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“…Of particular interest for the work reported here are studies on SAMs using metal underpotential deposition (UPD) as a probe. − In the UPD process, metal ions are reduced at certain foreign metal electrodes at potentials below their reversible reduction potential. This process often occurs for the first one to two monolayers of metal deposited at a potential up to several hundred millivolts below the reversible potential where bulk metal deposits. − The magnitude of the potential shift from the reversible reduction potential is indicative of the degree of thermodynamic stability that the heterometal affords the first one to two monolayers of electrochemically deposited metal.…”

Section: Introductionmentioning

confidence: 99%

Underpotential Deposition of Thallium, Lead, and Cadmium at Silver Electrodes Modified with Self-Assembled Monolayers of (3-Mercaptopropyl)trimethoxysilane

2007

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Investigation of the underpotential deposition (UPD) of three metals-Tl, Pb, and Cd-on Ag surfaces modified with self-assembled monolayers (SAMs) of (3-mercaptopropyl)trimethoxysilane (3MPT) is reported. On the basis of the observation of negative potential shifts for their UPD processes, Tl and Pb undergo UPD directly on the underlying Ag surface by insertion between the Ag-S bond. This process is proposed to occur by penetration of the 3MPT monolayer by hydrated metal ions through spaces in six-membered siloxane rings that form at the terminus of the 3MPT layer after hydrolysis and condensation. In contrast, Cd does not undergo similarly facile UPD at 3MPT-modified Ag electrodes due to a hydrated ion size too large to fit through these openings. The voltammetric evidence that suggests that the hydrated metal cation size, as described by the Stokes diameter, is the primary determinant of Ag electrode accessibility for UPD through the cross-linked 3MPT layer is further supported by molecular mechanics energy minimization computations of six-membered siloxane rings on each of the three low-index faces of Ag. Finally, the 3MPT monolayer is shown to be exceptionally stable to repeated UPD/stripping cycles of Tl and Pb in contrast to SAMs of similar thickness formed from normal alkanethiols.

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Underpotential Deposition and Stripping of Lead at Disorganized Monolayer‐Modified Gold Electrodes

Cited by 13 publications

References 26 publications

On the electrodeposition mechanism of Pb on copper substrate from a perchlorate solution studied by electrochemical quartz crystal microbalance

On the electrodeposition mechanism of Pb on copper substrate from a perchlorate solution studied by electrochemical quartz crystal microbalance

Anodic stripping voltammetry using graphite composite solid electrode

Underpotential Deposition of Thallium, Lead, and Cadmium at Silver Electrodes Modified with Self-Assembled Monolayers of (3-Mercaptopropyl)trimethoxysilane

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