A Study of the Underpotential Deposition of Lead on Gold by UV-Visible Differential Reflectance Spectroscopy

Motheo, Artur J.; González, Ernesto Rafael; Tremilliosi-Filho, Germano; Rakotondrainibé, A.; Léger, Jean‐Michel; Beden, B.; Lamy, C.

doi:10.1590/s0103-50531998000100006

Cited by 14 publications

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“…Further evidence for this being Pb upd at Au was provided by recording a cyclic voltammogram at a previously formed gold nanostructured electrode such as that shown in Figure d in a solution without KAuBr 4 but containing 0.5 mM Pb(CH 3 COO) 2 with 6.9 mM sodium acetate to keep the ionic strength similar to the deposition conditions (Figure b). The upd of lead can be seen by a minor cathodic process at 0.10 V and a more distinct peak at −0.30 V followed by oxidation peaks at 0.01 and 0.60 V. In the absence of the competing gold deposition process the upd processes can now be clearly seen and is similar with previous studies, although five pairs of peaks for Pb upd on Au single crystals were observed . A large hysteresis is observed between the first cathodic process and its anodic counterpart at the most positive potential and from previous work can be related to Pb adsorption on surface defects .…”

Section: Resultssupporting

confidence: 87%

Directing Nanostructure Formation of Gold through the In Situ Underpotential Deposition of a Secondary Metal for the Detection of Nitrite Ions

2017

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In this work, the underpotential deposition of metals such as copper and lead during the electrochemical deposition of gold is investigated to understand the influence that the incorporation of a second metal has on the morphology of gold nanostructures. The incorporation of Pb or Cu, even at concentrations as low as 0.2 %, significantly influences the morphology of the deposit, where the formation of elongated structures from a central gold structure is favored. These nanostructures are characterized by cyclic voltammetry, X‐ray diffraction, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy and are tested for their suitability as a sensing layer for the electrochemical detection of nitrite ions in aqueous solution. A limit of detection of 0.3 μM is achieved with a linear range up to 1 mM, which is adequate for the determination of nitrite contained within food products.

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Section: Resultssupporting

confidence: 87%

Directing Nanostructure Formation of Gold through the In Situ Underpotential Deposition of a Secondary Metal for the Detection of Nitrite Ions

2017

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“…On the other hand, while Cu upd on well-defined gold single crystals has been abundantly discussed in the literature (e.g, on Au(111), Au(110) or stepped Au-crystals), [60][61][62] fewer works have dealt with the deposition of copper on polycrystalline Au. [63][64][65] Most importantly, to the best of our knowledge, none of the above-mentioned studies unambiguously clarified whether it is possible to reach a complete coverage of the Au PC -surface with underpotentially deposited copper. Therefore, prior to performing the galvanic replacement experiments, we decided to first study the underpotential deposition of copper on polycrystalline gold.…”

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confidence: 84%

“…The stable voltammograms, plotted in Figure 5a, superimpose at potentials ≥0.31 V RHE and are again in good agreement with other CVs reported in the literature. 64 Moreover, their oxidation and reduction peaks can be related to the adsorption and desorption of Cu upd on Au-planes with certain crystallographic orientations; 60,61 more precisely, the oxidation currents at ≈0.4 and ≈0.6 V RHE (and corresponding reduction shoulders at ≈0.35 and ≈0.6 V RHE ) can be assigned to Au(111), while all three Au(100), Au(110) and Au(111) domains possibly contribute to the broader redox process at ≈0.65 V RHE . The sharply decreasing reduction currents at ≤ 0.27 V RHE , on the other hand, are due to copper bulk-deposition.…”

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confidence: 99%

Bulk-Palladium and Palladium-on-Gold Electrocatalysts for the Oxidation of Hydrogen in Alkaline Electrolyte

Henning

Herranz

Gasteiger

2014

J. Electrochem. Soc.

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The commercial feasibility of alkaline-exchange membrane fuel cells and electrolyzers passes by the development of hydrogen oxidation and evolution reaction (HOR/HER) catalysts featuring an activity and/or cost advantage over platinum, which remains the most active metal for these processes. Among these alternatives, Pd appears as a promising candidate, since its price is typically 2-3 fold lower than that of Pt. With this motivation, the first section of this study displays our attempts at quantifying the kinetic parameters of the HOR/HER on bulk Pd in 0.1 M NaOH, which were prevented by the simultaneous absorption of hydrogen into bulk palladium. We succeeded at circumventing this issue by depositing Pd-adlayers on a polycrystalline Au-substrate by galvanic displacement of underpotentially-deposited Cu or by electrochemical plating of Pd 2+ . The resulting surfaces appear to consist of three-dimensional Pd-structures of an unknown thickness that we believe to scale with the palladium coverage, θ Pd/Au . This last parameter is inversely proportional to the HOR/HER-activity of the Pd-on-Au surfaces, in agreement with numerous theoretical and experimental studies in acid media that correlate this effect to the tensile strain induced by the Au-substrate on the Pd-lattice. Proton-exchange membrane fuel cells (PEMFCs) fueled with hydrogen stored at 700 bar can attain energy densities in excess of 200 Wh · kg −1 (on a PEMFC system basis), making them excellent candidates for the propulsion of environmentally-benign, full range (≥ 300 miles) vehicles.1 However, the actual commercialization of PEMFC powered cars has been deterred by the lack of a hydrogen infrastructure and the high cost of the PEMFC. In this last respect, a significant fraction of the system's price is related to the costly platinum-based catalysts needed to catalyze the oxidation of hydrogen and the reduction of oxygen taking place at the FC anode and cathode, respectively.1-3 The kinetics of the oxygen reduction reaction (ORR) on Pt 4 are ≈7 orders of magnitude slower than those of the hydrogen oxidation reaction (HOR), 5 in agreement with the HOR 5 -and ORR 4 -exchange-current density (i 0 ) values of 4 ± 2 · 10 +2 mA · cmPt estimated by Neyerlin and coworkers (at 80• C and 100 kPa H 2 /air partial pressure). As such, the Pt-loading at the PEMFC's cathode (≈0.2-0.4 mg Pt · cm −2 ) is well above the ≤ 0.05 mg Pt · cm −2 required for the anodic HOR, and thus much research is being devoted to the development of more active and/or less expensive ORR catalysts.6-10 These include alloys of Pt with non-noble metals like Ni, Co or Cu (as well as their de-alloyed derivatives), and catalysts consisting of non-noble metal nanoparticles covered by one or a few monolayers of Pt (i.e., the so-called "core-shell" catalysts).Alternatively, operating a fuel cell in alkaline environment allows for the use a wider variety of potentially inexpensive, noblemetal free ORR-catalysts. Among these, certain materials based on Fe-, Co-and/or Cu-N 4 chelates (or equivalent no...

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“…In this electrolyte the formation of the copper sub-monolayer Brought to you by | Johns Hopkins University Authenticated Download Date | 2/6/15 8:01 PM is fully suppressed, copper ions are only deposited at steps and kinks of the substrate. Investigations with UV-visible reflectance spectroscopy at a polycrystalline gold electrode revealed the same effect [37]. But also the completion of the first copper monolayer is kinetically hindered.…”

Section: Discussionmentioning

confidence: 74%

The Under Potential Deposition of Cu on Au (111) in Nonaqueous Acetonitrile

Pekmez

Avci

Baumgärtel

et al. 2012

Zeitschrift Für Physikalische Chemie

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The underpotential deposition (UPD) of Copper on Au(111) in nonaqueous acetonitrile/perchlorate electrolyte has been investigated. The deposition mechanism is thereby strongly influenced by coadsorbed acetonitrile molecules and the stability of the solvation shell around the Cu(I) ions. The UPD mechanism obeys a two step mechanism even in presence of only none specifically adsorbing perchlorate ions. Thereby the first sub monolayer of copper is stabilized by coadsorbed acetonitrile molecules. However already 5% vol water content changes the structure within the double layer and consequently degrades the copper sub monolayer. At about 20% vol water content the Cu(I) ion/solvent complex is still stable. The reduction of Cu(I) ions from this complex is much faster compared to the reduction from the respective Cu(II) water complex.

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A Study of the Underpotential Deposition of Lead on Gold by UV-Visible Differential Reflectance Spectroscopy

Cited by 14 publications

References 0 publications

Directing Nanostructure Formation of Gold through the In Situ Underpotential Deposition of a Secondary Metal for the Detection of Nitrite Ions

Directing Nanostructure Formation of Gold through the In Situ Underpotential Deposition of a Secondary Metal for the Detection of Nitrite Ions

Bulk-Palladium and Palladium-on-Gold Electrocatalysts for the Oxidation of Hydrogen in Alkaline Electrolyte

The Under Potential Deposition of Cu on Au (111) in Nonaqueous Acetonitrile

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