On the structure of the Pt(100) and Pt(110) electrode surface in iodide solutions

Albers, Jan; Baltruschat, Helmut; Kamphausen, I.

doi:10.1016/0022-0728(95)04063-t

Cited by 18 publications

(13 citation statements)

References 20 publications

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“…Influence of halides ions adsorbed on single crystal electrodes of Pt was extensively reported by various groups (Solomun et al, 1984; Salaita et al, 1986; Shu and Bruckenstein, 1991; Vogel and Baltruschat, 1991; Oelgeklaus et al, 1994; Albers et al, 1995; DeSimone and Breen, 1995; Abruna et al, 1998; Arenz et al, 2003; Garcia-Araez et al, 2004, 2005, 2006a,b). AES/LEED investigations lead to the conclusion that the Cl − ion adsorption occurs on Pt (100) and Pt (111) surfaces at two different potentials, i.e., in the H upd and OH adsorption regions, respectively (Arruda et al, 2008).…”

Section: Non-recoverable Esa Losses With Halide Ion Adsorption and Acmentioning

confidence: 87%

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

et al. 2019

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Shape-controlled precious metal nanoparticles have attracted significant research interest in the recent past due to their fundamental and scientific importance. Because of their crystallographic-orientation-dependent properties, these metal nanoparticles have tremendous implications in electrocatalysis. This review aims to discuss the strategies for synthesis of shape-controlled platinum (Pt) and palladium (Pd) nanoparticles and procedures for the surfactant removal, without compromising their surface structural integrity. In particular, the electrocatalysis of oxygen reduction reaction (ORR) on shape-controlled nanoparticles (Pt and Pd) is discussed and the results are analyzed in the context of that reported with single crystal electrodes. Accepted theories on the stability of precious metal nanoparticle surfaces under electrochemical conditions are revisited. Dissolution, reconstruction, and comprehensive views on the factors that contribute to the loss of electrochemically active surface area (ESA) of nanoparticles leading to an inevitable decrease in ORR activity are presented. The contribution of adsorbed electrolyte anions, in-situ generated adsorbates and contaminants toward the ESA reduction are also discussed. Methods for the revival of activity of surfaces contaminated with adsorbed impurities without perturbing the surface structure and its implications to electrocatalysis are reviewed.

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Section: Non-recoverable Esa Losses With Halide Ion Adsorption and Acmentioning

confidence: 87%

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

et al. 2019

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“…e. g. by AC voltammetry, [16] also a detailed determination of the thermodynamic Gibbs surface excess was reported for several systems [17–21] . On single‐crystal surfaces, the adsorbed ions usually form an ordered adlayer phase, with a structure and packing density depending on potential, as shown by LEED, STM and SXS [22–32] …”

Section: Introductionmentioning

confidence: 98%

“…[17][18][19][20][21] On single-crystal surfaces, the adsorbed ions usually form an ordered adlayer phase, with a structure and packing density depending on potential, as shown by LEED, STM and SXS. [22][23][24][25][26][27][28][29][30][31][32] Much fewer studies dealt with the rate of the adsorption process, particularly on single crystal surfaces. Whereas the metallic adsorption systems ("underpotential deposition", upd) is typically characterized by an attractive interaction between the adsorbed atoms, the adsorption of anions (and also hydrogen) is characterised by repulsive interaction, giving rise to broader adsorption peaks in cyclic voltammetry.…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Iodide and Bromide on Au(111) Electrodes from Aprotic Electrolytes: Role of the Solvent

2020

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The adsorption of iodide and bromide ions on Au(111) singlecrystal electrodes in three organic solvents [propylene carbonate (PC), diglyme (DG), and dimethyl sulfoxide (DMSO)] was studied by differential capacity measurements, cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The anion adsorption charge in DMSO is approximately half as large as in propylene carbonate and that in water. Quantification of the adsorbed iodide amount from XPS spectra confirms the coverage estimated from the adsorption charge in CVs. As expected, the rate of anion adsorption on Au(111) is higher for I À than for Br À due to better solvation of the latter. The extent of anion adsorption on Au(111) electrode decreases and the corresponding adsorption rate decreases in the solvent order H 2 O > PC > DG > DMSO. Since the donor number (DN) of the solvent increases in the same order (PC < DG < DMSO), we assume that it plays a decisive role since it determines the chemical interaction of the solvent with the metal surface. Moreover, the adsorption rate of iodide and the extent of its adsorption is increased with increasing water content in PC and DMSO. This effect, and the much higher adsorption rate in water is explained by the closer approach of the solvated halogen ion to the surface and the resulting stronger interaction of the transition state with the electrode.

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“…[10][11][12][13][14][15][16][17][18][19][20][21] Feliu et al, Abruna et al, and others have extensively investigated the influence of halides (I − , Br − , Cl − ) on platinum single crystal electrodes. [22][23][24][25][26][27][28][29][30][31][32][33][34][35] Most of the available surface sensitive techniques were used to elucidate adsorbate coverage and structure. Such techniques, including auger electron spectroscopy (AES), low energy electron diffraction (LEED), second harmonic generation (SHG), surface X-ray scattering (SXS), electrochemical scanning tunneling microscope (ESTM) 31,34 and electrochemical quartz crystal microbalance (EQCM), used to investigate anion adsorption have offered significant insight on the dependence of adsorption process on exposed single crystal orientations.…”

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confidence: 99%

Recovery of Active Surface Sites of Shape-Controlled Platinum Nanoparticles Contaminated with Halide Ions and Its Effect on Surface-Structure

Devivaraprasad¹,

Kar²,

Leuaa³

et al. 2017

J. Electrochem. Soc.

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The interaction of halide ions (I − , Br − , Cl − ) with well-cleaned faceted platinum (nanocube, cuboctahedral) nanoparticles and platinum polycrystalline is investigated in 0.5 M H 2 SO 4 electrolyte. Under electrochemical conditions, the Pt surface gets poisoned with halide ad-atoms and it causes the attenuation of both hydrogen adsorption/desorption in the lower potential region (0.06-0.4 V) and electroxidation of Pt nanoparticles in the higher potential region (0.6-1.2 V). Above certain concentration (5 × 10 −6 M), the strongly adsorbing I − ions mask the H upd features. On the other hand, Br − and Cl − ions alter the peak features in the H upd region, those are characteristic of different Pt surface sites. On excursion to higher potentials (∼>1.2 V), concurrent halogen evolution, Pt oxidation, and oxygen evolution are observed; the increase in peak intensity in the H upd region reflects the reconstruction of the Pt surface. To remove the adsorbed halide ions from the Pt surface, an in-situ potentiostatic method is employed, which involves holding the working electrode at ∼0.03 V in 0.1 M NaOH solution. The cleanliness and retention of surface-structure are confirmed from the voltammograms recorded in the test electrolyte and the recovery of oxygen reduction reaction (ORR) activity after cleaning the Br − ion-contaminated Pt surface supports this conjecture. Anions specifically adsorbed on precious metal surfaces adversely impact several electrochemical reactions including oxidation/ reduction, metal deposition, corrosion and dissolution.1-6 Catalyst poisoning by the adsorbed anions (halides, sulfates and others) is a well-known phenomenon and it decreases the activity of electrocatalysts; for example, in fuel-cell, batteries and electrolyzers. 7,8 Especially platinum, a material for catalyzing a variety of electrochemical reactions, is prone to get poisoned in the presence of adatoms/adsorbates/solution anions under electrochemical conditions. Thus, oxygen reduction reaction (ORR) in fuel cells is affected by the adsorbed species or impurities and it is highly dependent on the cleanliness and surface structure of the catalyst. [9][10][11][12][13] In hydrogen-bromine fuel cells, bromides and bromine species migrate across the membrane and poison the hydrogen-electrode catalyst; moreover, Pt dissolves in Br − ion-containing solutions. 22-35 Most of the available surface sensitive techniques were used to elucidate adsorbate coverage and structure. Such techniques, including auger electron spectroscopy (AES), low energy electron diffraction (LEED), second harmonic generation (SHG), surface X-ray scattering (SXS), electrochemical scanning tunneling microscope (ESTM) 31,34 and electrochemical quartz crystal microbalance (EQCM), used to investigate anion adsorption have offered significant insight on the dependence of adsorption process on exposed single crystal orientations. Thus, AES/LEED studies revealed that Cl − ion adsorption occurs on Pt(100) surface at lower potential than that with Pt(111) surfaces, indi...

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On the structure of the Pt(100) and Pt(110) electrode surface in iodide solutions

Cited by 18 publications

References 20 publications

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

Adsorption of Iodide and Bromide on Au(111) Electrodes from Aprotic Electrolytes: Role of the Solvent

Recovery of Active Surface Sites of Shape-Controlled Platinum Nanoparticles Contaminated with Halide Ions and Its Effect on Surface-Structure

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