Partial charge transfer in the underpotential deposition of metals

Salié, G.; Bartels, Klaus

doi:10.1016/0022-0728(88)80056-1

Cited by 17 publications

(21 citation statements)

References 9 publications

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“…This causes progressive changes to the gold surface due to the formation of Hg-Au amalgam and ultimately results in the Hg peak potential shift and Hg peak current intensity lowering. 20 However, Hg levels in marine waters are sufficiently low for the deposition to occur in the UPD regime.…”

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confidence: 99%

“…UPD results in a submonolayer to monolayer of stable adsorbed Hg whose structure is strongly dependent on the crystallographic plane of gold. , At higher Hg concentrations or after long deposition times, Hg becomes fully reduced to Hg(0) and starts to diffuse into the gold substrate. This causes progressive changes to the gold surface due to the formation of Hg–Au amalgam and ultimately results in Hg peak potential shift and Hg peak current intensity lowering . However, Hg levels in marine waters are sufficiently low for the deposition to occur in the UPD regime.…”

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confidence: 99%

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In Situ Voltammetric Sensor of Potentially Bioavailable Inorganic Mercury in Marine Aquatic Systems Based on Gel-Integrated Nanostructured Gold-Based Microelectrode Arrays

et al. 2021

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The development and field validation of newly designed nanostructured gold-plated gelintegrated microelectrode arrays (Au-GIME) applied to the direct in situ Square Wave Anodic Stripping Voltammetry (SWASV) quantification of the potentially bioavailable inorganic mercury (Hg(II)) species in coastal area are presented. The Au-GIME consists of arrays of 100 to 500 interconnected iridium (Ir)-based microdisks that are electroplated with renewable Au nanoparticles (AuNP) or Au nanofilaments (AuNF) and covered with an agarose gel. The gel protects the sensor surface from fouling and ensures that mass transport of analytes toward the sensor surface is by pure diffusion only and therefore independent of the ill-controlled convective conditions of the media. The responses of these sensors to direct SWASV measurements of inorganic Hg(II) at near-neutral pH were investigated first in synthetic media, then in UV irradiated marine samples. The analytical responses were found to be correlated to the number of interconnected microelectrodes and the morphology of the nanostructured Au deposits, and independent of the media composition for chloride concentration  0.2M (salinity S  13) and pH ranging from 7 to 8.5. The AuNF-GIMEs have detection and quantification limits at the low pM level, fulfilling the requirement of sentinel tools for real-time monitoring of the dynamic fraction of Hg(II) in coastal area. The AuNF-GIMEs were incorporated in an in-house advanced multi-channel sensing probe for remote in situ highresolution trace metal monitoring. Field evaluation and validation were successfully performed as 2 part of a field study in the Arcachon Bay (France), from which environmental data are presented. This work marks the first time that an autonomous electrochemical sensing probe successfully measures Hg(II) and its hourly temporal variation in situ without chemical modification of the sample.

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In Situ Voltammetric Sensor of Potentially Bioavailable Inorganic Mercury in Marine Aquatic Systems Based on Gel-Integrated Nanostructured Gold-Based Microelectrode Arrays

et al. 2021

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“…According to the equation Δ E p = 2.3 RT / nF , we estimate that a two-electron transfer processes ( n = 2) is involved in the deposition and oxidation of Hg in the negative and positive scans, respectively (eq ). , …”

Section: Resultsmentioning

confidence: 99%

Real-Time Plasmonic Monitoring of Single Gold Amalgam Nanoalloy Electrochemical Formation and Stripping

Wang

Fossey

et al. 2016

ACS Appl. Mater. Interfaces

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Direct electrodeposition of mercury onto gold nanorods on an ITO substrate, without reducing agents, is reported. The growth of single gold amalgam nanoalloy particles and subsequent stripping was monitored in real-time monitoring by plasmonic effects and single-nanoparticle dark-field spectroelectrochemistry techniques. Time-dependent scattering spectral information conferred insight into the growth and stripping mechanism of a single nanoalloy particle. Four critical stages were observed: First, rapid deposition of Hg atoms onto Au nanorods; second, slow diffusion of Hg atoms into Au nanorods; third, prompt stripping of Hg atoms from Au nanorods; fourth, moderate diffusion from the inner core of Au nanorods. Under high Hg(2+) concentrations, homogeneous spherical gold amalgam nanoalloys were obtained. These results demonstrate that the morphology and composition of individual gold amalgam nanoalloys can be precisely regulated electrochemically. Moreover, gold amalgam nanoalloys with intriguing optical properties, such as modulated plasmonic lifetimes and quality factor Q, could be obtained. This may offer opportunities to extend applications in photovoltaic energy conversion and chemical sensing.

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“…Salié and Bartels [17][18][19][20] have considered the process of Hg UPD from Hg(I) and Hg(II) perchloric acid solutions as proceeding in partial charge-transfer steps. The authors, in order to explain different experimental results, have assumed two-step process.…”

Section: Deposition and Underpotential Deposition Of Hg On Various Elmentioning

confidence: 99%

Electrochemistry of Mercury

Orlik

Galus

2006

Encyclopedia of Electrochemistry

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The sections in this article are Double‐layer Properties of Hg /Water Interface Potential of Zero Charge Surface Charge Density and Capacitive Current Experimental and Theoretical Studies of the Hg /Water Interface Double‐layer Properties of Hg /Nonaqueous Media Interface Adsorption and Electrode Reactions at Hg Surface Deposition and Underpotential Deposition of Hg on Various Electrodes Underpotential Deposition of Mercury on Gold Electrodes Film Electrodes and Related Hg Electrodes Adsorption and Electrode Reactions of Inorganic Ions and Coordination Compounds of Metal Ions Analytical Applications Adsorption and Electrode Reactions Involving Organic Compounds Organic Compounds Containing Sulfur, Selenium, and Tellurium Organic Nitrogen Compounds Indicators and Dyes Vitamins and Antibiotics Enzymes and Coenzymes Other Organic Compounds Analytical Aspects of Adsorption of Organic Compounds Ammonium and Quaternary‐substituted Ammonium Amalgams

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Partial charge transfer in the underpotential deposition of metals

Cited by 17 publications

References 9 publications

In Situ Voltammetric Sensor of Potentially Bioavailable Inorganic Mercury in Marine Aquatic Systems Based on Gel-Integrated Nanostructured Gold-Based Microelectrode Arrays

In Situ Voltammetric Sensor of Potentially Bioavailable Inorganic Mercury in Marine Aquatic Systems Based on Gel-Integrated Nanostructured Gold-Based Microelectrode Arrays

Real-Time Plasmonic Monitoring of Single Gold Amalgam Nanoalloy Electrochemical Formation and Stripping

Electrochemistry of Mercury

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