Bromide adsorption on Pt(100): Rotating ring-Pt(100) disk electrode and surface X-ray scattering measurements

Nenad M. Marković; Chris A. Lucas; Hubert A. Gasteiger; Philip N. Ross

doi:10.1016/0039-6028(96)00721-2

Bromide adsorption on Pt(100): Rotating ring-Pt(100) disk electrode and surface X-ray scattering measurements

Nenad M. Marković, Chris A. Lucas, Hubert A. Gasteiger, Philip N. Ross

Research output: Contribution to journal › Article › peer-review

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Abstract

The rotating ring-disk electrode technique with a Pt(100) single crystal disk electrode is used to establish both the bromide adsorption isotherm and the electrosorption valency on Pt(100). In 0.1M HC1O₄ with ∼10^-4 Br^-. bromide adsorption begins at about -0.25 V and reaches a coverage of ∼0.42 ML at 0.5 V; the electrosorption valency is essentially unity. The major peak in the voltammetry at ∼-0.1 V is the simultaneous adsorption/desorption of hydrogen and desorption/adsorption of Br^-. By subtracting the Br^- flux we are able to deconvolute the charge for the hydrogen adsorption in the presence of Br^-. The saturation coverage is about the same as in solution free of Br^- ∼210 μC cm^-2, but the potential region for the onset of adsorption is shifted negatively by 0.35 V due to the competition with Br^- adsorption. The reversible pseudocapacitive feature recorded in 0.1M HC1O₄ at 0.175 ≲E≲0.375 V should be assigned to the reversible adsorption of hydroxyl species. Despite the inability to detect any in-plane superlattice peaks corresponding to a long-range ordered structure in the Br adlayer, the x-ray scattering data provide information about the surface normal structure and local bonding sites for the Br adlayer on Pt(100).

Original language	English
Pages (from-to)	229-240
Number of pages	12
Journal	Surface Science
Volume	365
Issue number	2
DOIs	https://doi.org/10.1016/0039-6028(96)00721-2
State	Published - 20 Sep 1996
Externally published	Yes

Keywords

Bromine
Electrochemical methods
Low index single crystal surfaces
Solid-liquid interfaces
Superlattices
Surface structure
X-ray scattering

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10.1016/0039-6028(96)00721-2

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@article{1e05bfbe967d4c8d9afb427ddaced9f7,

title = "Bromide adsorption on Pt(100): Rotating ring-Pt(100) disk electrode and surface X-ray scattering measurements",

abstract = "The rotating ring-disk electrode technique with a Pt(100) single crystal disk electrode is used to establish both the bromide adsorption isotherm and the electrosorption valency on Pt(100). In 0.1M HC1O4 with ∼10-4 Br-. bromide adsorption begins at about -0.25 V and reaches a coverage of ∼0.42 ML at 0.5 V; the electrosorption valency is essentially unity. The major peak in the voltammetry at ∼-0.1 V is the simultaneous adsorption/desorption of hydrogen and desorption/adsorption of Br-. By subtracting the Br- flux we are able to deconvolute the charge for the hydrogen adsorption in the presence of Br-. The saturation coverage is about the same as in solution free of Br- ∼210 μC cm-2, but the potential region for the onset of adsorption is shifted negatively by 0.35 V due to the competition with Br- adsorption. The reversible pseudocapacitive feature recorded in 0.1M HC1O4 at 0.175 ≲E≲0.375 V should be assigned to the reversible adsorption of hydroxyl species. Despite the inability to detect any in-plane superlattice peaks corresponding to a long-range ordered structure in the Br adlayer, the x-ray scattering data provide information about the surface normal structure and local bonding sites for the Br adlayer on Pt(100).",

keywords = "Bromine, Electrochemical methods, Low index single crystal surfaces, Solid-liquid interfaces, Superlattices, Surface structure, X-ray scattering",

author = "Markovi{\'c}, {Nenad M.} and Lucas, {Chris A.} and Gasteiger, {Hubert A.} and Ross, {Philip N.}",

note = "Funding Information: The authors are greatly indebted to the invaluable assistance of Lee Johnson who oriented, cut, and polished the crystal used in this study. Furthermore, he and Frank Zucca ensured that the rotator kept rotating --not a small task, for which we would like to express our thanks. We would also like to thank B. Zhang and S. Bennett for their assistance with beamline X10A at the NSLS.This work was supported by the Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences Division (MSD) of the US Department of Energy under contract No. DE-AC03-76SF00098. Research was carried out at in part at the NSLS, Brookhaven National Laboratory which is supported by the MSD and Division of Chemical Sciences (DCS), US DOE under contract No. DE-AC02-76CH0006.",

year = "1996",

month = sep,

day = "20",

doi = "10.1016/0039-6028(96)00721-2",

language = "English",

volume = "365",

pages = "229--240",

journal = "Surface Science",

issn = "0039-6028",

publisher = "Elsevier B.V.",

number = "2",

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TY - JOUR

T1 - Bromide adsorption on Pt(100)

T2 - Rotating ring-Pt(100) disk electrode and surface X-ray scattering measurements

AU - Marković, Nenad M.

AU - Lucas, Chris A.

AU - Gasteiger, Hubert A.

AU - Ross, Philip N.

N1 - Funding Information: The authors are greatly indebted to the invaluable assistance of Lee Johnson who oriented, cut, and polished the crystal used in this study. Furthermore, he and Frank Zucca ensured that the rotator kept rotating --not a small task, for which we would like to express our thanks. We would also like to thank B. Zhang and S. Bennett for their assistance with beamline X10A at the NSLS.This work was supported by the Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences Division (MSD) of the US Department of Energy under contract No. DE-AC03-76SF00098. Research was carried out at in part at the NSLS, Brookhaven National Laboratory which is supported by the MSD and Division of Chemical Sciences (DCS), US DOE under contract No. DE-AC02-76CH0006.

PY - 1996/9/20

Y1 - 1996/9/20

N2 - The rotating ring-disk electrode technique with a Pt(100) single crystal disk electrode is used to establish both the bromide adsorption isotherm and the electrosorption valency on Pt(100). In 0.1M HC1O4 with ∼10-4 Br-. bromide adsorption begins at about -0.25 V and reaches a coverage of ∼0.42 ML at 0.5 V; the electrosorption valency is essentially unity. The major peak in the voltammetry at ∼-0.1 V is the simultaneous adsorption/desorption of hydrogen and desorption/adsorption of Br-. By subtracting the Br- flux we are able to deconvolute the charge for the hydrogen adsorption in the presence of Br-. The saturation coverage is about the same as in solution free of Br- ∼210 μC cm-2, but the potential region for the onset of adsorption is shifted negatively by 0.35 V due to the competition with Br- adsorption. The reversible pseudocapacitive feature recorded in 0.1M HC1O4 at 0.175 ≲E≲0.375 V should be assigned to the reversible adsorption of hydroxyl species. Despite the inability to detect any in-plane superlattice peaks corresponding to a long-range ordered structure in the Br adlayer, the x-ray scattering data provide information about the surface normal structure and local bonding sites for the Br adlayer on Pt(100).

AB - The rotating ring-disk electrode technique with a Pt(100) single crystal disk electrode is used to establish both the bromide adsorption isotherm and the electrosorption valency on Pt(100). In 0.1M HC1O4 with ∼10-4 Br-. bromide adsorption begins at about -0.25 V and reaches a coverage of ∼0.42 ML at 0.5 V; the electrosorption valency is essentially unity. The major peak in the voltammetry at ∼-0.1 V is the simultaneous adsorption/desorption of hydrogen and desorption/adsorption of Br-. By subtracting the Br- flux we are able to deconvolute the charge for the hydrogen adsorption in the presence of Br-. The saturation coverage is about the same as in solution free of Br- ∼210 μC cm-2, but the potential region for the onset of adsorption is shifted negatively by 0.35 V due to the competition with Br- adsorption. The reversible pseudocapacitive feature recorded in 0.1M HC1O4 at 0.175 ≲E≲0.375 V should be assigned to the reversible adsorption of hydroxyl species. Despite the inability to detect any in-plane superlattice peaks corresponding to a long-range ordered structure in the Br adlayer, the x-ray scattering data provide information about the surface normal structure and local bonding sites for the Br adlayer on Pt(100).

KW - Bromine

KW - Electrochemical methods

KW - Low index single crystal surfaces

KW - Solid-liquid interfaces

KW - Superlattices

KW - Surface structure

KW - X-ray scattering

UR - http://www.scopus.com/inward/record.url?scp=0030242985&partnerID=8YFLogxK

U2 - 10.1016/0039-6028(96)00721-2

DO - 10.1016/0039-6028(96)00721-2

M3 - Article

AN - SCOPUS:0030242985

SN - 0039-6028

VL - 365

SP - 229

EP - 240

JO - Surface Science

JF - Surface Science

IS - 2

ER -

Bromide adsorption on Pt(100): Rotating ring-Pt(100) disk electrode and surface X-ray scattering measurements

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