Underpotential Deposition

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Richard G. Compton - One of the best experts on this subject based on the ideXlab platform.

Ezequiel P. M. Leiva - One of the best experts on this subject based on the ideXlab platform.

  • Moïse Haïssinsky: The Discoverer of Underpotential Deposition
    ChemElectroChem, 2017
    Co-Authors: Fritz Scholz, Ezequiel P. M. Leiva
    Abstract:

    Underpotential Deposition (upd) is a highly important topic within electrochemistry. Its discovery and early development are tightly connected with the rise of radiochemistry at the beginning of the last century and the nuclear weapon and atomic energy programs during and after World War II. Only later it reached fundamental electrochemistry in civil research institutes. Moise Haissinsky played a key role in discovering upd, when he worked at “L'Institut du Radium” in Paris, starting under the directorship of Marie Sklodowska-Curie. Among all of the scientists who have to be named in a history of upd, Moise Haissinsky is the least well known, because his research was later almost entirely in the field of radiochemistry. In this paper, he is remembered for his contributions to electrochemistry and his life is described in more detail.

  • Applications of Underpotential Deposition on Bulk Electrodes as a Model System for Electrocatalysis
    Underpotential Deposition, 2015
    Co-Authors: O. A. Oviedo, Luis Reinaudi, S.g. García, Ezequiel P. M. Leiva
    Abstract:

    The Underpotential Deposition (upd) of metals may modify the catalytic activity of substrates in several ways. For the sake of simplicity, we divide the types of impacts that upd metals can produce in four types, although they all can in principle be acting on a given reaction at the same time.

  • Underpotential Deposition: From planar surfaces to nanoparticles
    Surface Science, 2015
    Co-Authors: O. A. Oviedo, Patricio Vélez, Vicente A. Macagno, Ezequiel P. M. Leiva
    Abstract:

    Abstract An overview is given of selected theoretical, experimental and computer simulation research on thermodynamic modeling applied to the metal Underpotential Deposition. Focus is made mainly on the last 20 years. The upd -theory on planar surfaces is revisited and the thermodynamic framework is extended to consider Underpotential Deposition on nanoparticles and to include anion coadsorption, solvation and double layer charging. Results from molecular dynamics and Monte Carlo simulations are shown for systems of experimental interest. At the end some perspectives for further advanced modeling of the present problem are given.

  • The limits of Underpotential Deposition in the nanoscale
    Electrochemistry Communications, 2012
    Co-Authors: O. A. Oviedo, Luis Reinaudi, Ezequiel P. M. Leiva
    Abstract:

    Abstract A thermodynamic model predicting the disappearance of the Underpotential Deposition phenomenon in the limit of small nanoparticles is proposed and developed for selected families of geometric bodies. The key parameters are the binding energy of adatoms on the flat foreign substrate and at the edges of the nanoparticle.

  • The Underpotential Deposition that should not be : Cu(1x1) on Au(111)
    Electrochemistry Communications, 2012
    Co-Authors: Patricio Vélez, Ezequiel P. M. Leiva, Angel Cuesta, V. A. Macagno
    Abstract:

    Abstract Underpotential Deposition of copper on Au(111) is analyzed in the light of first-principles calculations. The existence of a 1 × 1 Cu monolayer on Au(111) at Underpotentials can be only understood taking into account the free energy excess delivered by the adsorption of sulfate anions. While a naked copper pseudomorphic monolayer results thermodynamically less stable than bulk copper, accounting for the interaction with sulfate ions delivers an Underpotential shift which is comparable with the experimental value.

Damien W. M. Arrigan - One of the best experts on this subject based on the ideXlab platform.

  • determination of trace metals by Underpotential Deposition stripping voltammetry at solid electrodes
    Trends in Analytical Chemistry, 2005
    Co-Authors: Gregoire Herzog, Damien W. M. Arrigan
    Abstract:

    Abstract We introduce the behaviour and applications of Underpotential Deposition (UPD) and its combination with stripping voltammetry (UPD–SV) of metal analytes at solid-electrode surfaces as an important analytical strategy for trace-metal determinations. We review the principles of UPD together with model metal/electrode systems, and discuss analytical utility, including achievement of limits of detection (LODs) and applications to a variety of sample matrices. We present an approach to the alleviation of sample-matrix effects by using surface-protective disorganised monolayer coatings. Finally, we also present the outlook for UPD–SV as an electroanalytical tool.

  • Determination of trace metals by Underpotential Deposition–stripping voltammetry at solid electrodes
    TrAC Trends in Analytical Chemistry, 2005
    Co-Authors: Gregoire Herzog, Damien W. M. Arrigan
    Abstract:

    Abstract We introduce the behaviour and applications of Underpotential Deposition (UPD) and its combination with stripping voltammetry (UPD–SV) of metal analytes at solid-electrode surfaces as an important analytical strategy for trace-metal determinations. We review the principles of UPD together with model metal/electrode systems, and discuss analytical utility, including achievement of limits of detection (LODs) and applications to a variety of sample matrices. We present an approach to the alleviation of sample-matrix effects by using surface-protective disorganised monolayer coatings. Finally, we also present the outlook for UPD–SV as an electroanalytical tool.

  • Underpotential Deposition of Copper at Mercaptoalkane Sulfonate-Coated Polycrystalline Gold
    Electroanalysis, 2001
    Co-Authors: Damien W. M. Arrigan, Tabassum Iqbal, Mark J. Pickup
    Abstract:

    Underpotential Deposition (UPD) of copper from aqueous sulfuric acid solution onto polycrystalline gold electrodes coated with 2-mercaptoethane sulfonate (MES) or 3-mercapto-1-propane sulfonate (MPS) films has been studied. On the basis of peak shape, the UPD reduction process was inhibited by the organosulfonate film, with the greater inhibition being observed for the MPS film. The inhibitory affects in the UPD can be overcome by Deposition at a constant Underpotential (0.00 V vs. SCE) for a set time. After this set time (≥60 s) the charge for stripping of the Underpotential deposit was equivalent to the charge recorded for UPD stripping at the bare polycrystalline gold surface.

G. A. Ragoisha - One of the best experts on this subject based on the ideXlab platform.

  • Underpotential Deposition of lead onto bi2te3 te heterostructures
    Electrochemistry Communications, 2018
    Co-Authors: A.s. Bakavets, G. A. Ragoisha, Y.m. Aniskevich, E.a. Streltsov
    Abstract:

    Abstract Underpotential Deposition of lead proceeds on Bi2Te3 and Te components of Bi2Te3/Te heterostructures. From cyclic voltammetry and cyclic potentiodynamic nanogravimetry, the cathodic Deposition and anodic oxidation of lead adlayer on Bi2Te3 are chemically reversible in stationary cycles, while a small fraction of Pb adlayer on tellurium transforms into PbTe in each cycle, which results in the emergent voltammetric response of lead upd on PbTe. The latter is helpful for disclosure of tellurium coDeposition with bismuth telluride. Besides being a handy analytical tool, the upd of lead acts as precise batcher for introduction of ultra-small amount of lead and lead telluride onto bismuth telluride surface.

  • Underpotential Deposition of lead onto Bi2Te3/Te heterostructures
    Electrochemistry Communications, 2018
    Co-Authors: A.s. Bakavets, G. A. Ragoisha, Y.m. Aniskevich, Eugene A. Streltsov
    Abstract:

    Abstract Underpotential Deposition of lead proceeds on Bi2Te3 and Te components of Bi2Te3/Te heterostructures. From cyclic voltammetry and cyclic potentiodynamic nanogravimetry, the cathodic Deposition and anodic oxidation of lead adlayer on Bi2Te3 are chemically reversible in stationary cycles, while a small fraction of Pb adlayer on tellurium transforms into PbTe in each cycle, which results in the emergent voltammetric response of lead upd on PbTe. The latter is helpful for disclosure of tellurium coDeposition with bismuth telluride. Besides being a handy analytical tool, the upd of lead acts as precise batcher for introduction of ultra-small amount of lead and lead telluride onto bismuth telluride surface.

  • Underpotential Deposition of lead onto Bi2Te3/Te heterostructures
    Elsevier, 2018
    Co-Authors: A.s. Bakavets, G. A. Ragoisha, Y.m. Aniskevich, E.a. Streltsov
    Abstract:

    Underpotential Deposition of lead proceeds on Bi2Te3 and Te components of Bi2Te3/Te heterostructures. From cyclic voltammetry and cyclic potentiodynamic nanogravimetry, the cathodic Deposition and anodic oxidation of lead adlayer on Bi2Te3 are chemically reversible in stationary cycles, while a small fraction of Pb adlayer on tellurium transforms into PbTe in each cycle, which results in the emergent voltammetric response of lead upd on PbTe. The latter is helpful for disclosure of tellurium coDeposition with bismuth telluride. Besides being a handy analytical tool, the upd of lead acts as precise batcher for introduction of ultra-small amount of lead and lead telluride onto bismuth telluride surface. Keywords: Underpotential Deposition, ElectroDeposition, Bismuth telluride, Lead, Tellurium, Lead tellurid

  • Potentiodynamic Electrochemical Impedance Spectroscopy for Underpotential Deposition Processes
    Electroanalysis, 2015
    Co-Authors: G. A. Ragoisha
    Abstract:

    Potentiodynamic electrochemical impedance spectroscopy makes available, from cyclic potential scan combined with frequency response acquisition, a set of potentiodynamic profiles of characteristic electrochemical variables in addition to a voltammetric profile. Especially informative in the Underpotential Deposition is the double layer capacitance profile which characterises alterations of the interface status during the potential scan. Potentiodynamic profiles of charge transfer resistance and Warburg coefficient present complementary information about faradaic part of the electrochemical response. Profiles of adsorption capacitance are available in the reversible UPD.

  • Potentiodynamic electrochemical impedance spectroscopy. Copper Underpotential Deposition on gold
    Electrochemistry Communications, 2003
    Co-Authors: G. A. Ragoisha, A. S. Bondarenko
    Abstract:

    Copper Underpotential Deposition on polycrystalline gold was examined by potentiodynamic electrochemical impedance spectroscopy (PDEIS). The time evolution of the ac response was acquired as 3D plots of frequency response versus applied potential, and these data were later processed with an equivalent circuit analyser built into the virtual spectrometer. The dependences of the equivalent circuit parameters on potential revealed different responses of nitrate and sulphate. Nitrate adsorption pseudocapacitance, and the inverse of the adsorption pseudoresistance, both exhibited peaks in a narrow range of Cu monolayer growth, while sulphate affected a wider potential range and gave two desorption peaks in the anodic scan. Intrinsic irreversibility of the constituent processes was revealed by cyclic redox transformations of the Cu monolayer.

M. V. Sangaranarayanan - One of the best experts on this subject based on the ideXlab platform.

  • Underpotential Deposition of metals – Progress and prospects in modelling
    Journal of Chemical Sciences, 2005
    Co-Authors: V. Sudha, M. V. Sangaranarayanan
    Abstract:

    Underpotential Deposition (UPD) of metals is analysed from the perspective of phenomeno-logical and statistical thermodynamic considerations; the parameters influencing the UPD shift have been quantitatively indicated using a general formalism. The manner in which the macroscopic properties pertaining to the depositing ions and solvent dipoles and the nature of the metallic substrate influence the UPD process are highlighted; earlier correlations of the UPD shift with the work function differences are rationalised. Anion-induced phase transitions which manifest as sharp peaks in experimental cyclic voltammograms are discussed using statistical thermodynamic models.

  • Development of electrochemical supercapacitors using Underpotential Deposition of thallium on silver
    Indian journal of chemistry. Sect. A: Inorganic physical theoretical & analytical, 2005
    Co-Authors: T. C. Girija, M. V. Sangaranarayanan
    Abstract:

    The design of electrochemical supercapacitors exploiting the concept of Underpotential Deposition (UPD) is demonstrated using the UPD of thallium on silver as an illustrative example. The specific capacitance is deduced as 3.45×10 2 Farads g - 1 from cyclic voltammetric studies employing the roughness factor for calculating the electroactive surface area.

  • Underpotential Deposition of metals - : Progress and prospects in modelling
    Journal of Chemical Sciences, 2005
    Co-Authors: V. Sudha, M. V. Sangaranarayanan
    Abstract:

    Underpotential Deposition (UPD) of metals is analysed from the perspective of phenomeno - logical and statistical thermodynamic considerations; the parameters influencing the UPD shift have been quantitatively indicated using a general formalism. The manner in which the macroscopic properties per- taining to the depositing ions and solvent dipoles and the nature of the metallic substrate influence the UPD process are highlighted; earlier correlations of the UPD shift with the work function differences are rationalised. Anion-induced phase transitions which manifest as sharp peaks in experimental cyclic vol t- ammograms are discussed using statistical thermodynamic models.

  • Underpotential Deposition of Metals from Thermodynamic and Structural Considerations. 2. Nonaqueous Solvents
    The Journal of Physical Chemistry B, 2003
    Co-Authors: V. Sudha, M. V. Sangaranarayanan
    Abstract:

    The Underpotential Deposition (UPD) shifts of different metallic couples in acetonitrile and propylene carbonate are estimated using work function differences, lattice coordination numbers, and ads...

  • Underpotential Deposition of Metals: Structural and Thermodynamic Considerations
    The Journal of Physical Chemistry B, 2002
    Co-Authors: V. Sudha And, M. V. Sangaranarayanan
    Abstract:

    The dependence of Underpotential Deposition (UPD) shift on work function differences, lattice coordination numbers, solvent desorption energies, and surface coverages is analyzed. The transport processes that govern monolayer formation and bulk Deposition are incorporated. The parameteric dependence of the UPD shift on different thermodynamic quantities and adsorbate charge densities is reported. The validity of the formalism is demonstrated by comparison with the experimental data.

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