Adlayer Structures of Chlorine, Bromine, and Iodine on Cu(111) Electrode in Solution:  In-Situ STM and ex-Situ LEED Studies

Inukai, Junji; Osawa, Yohei; Itaya, Kingo

doi:10.1021/jp982952l

Cited by 84 publications

(87 citation statements)

References 32 publications

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“…Iodine adsorption on Cu (1 1 1) and Cu(1 0 0) LEED [8,9] and STM studies [10] have reported the formation of a ð ffiffi ffi…”

Section: Methodsmentioning

confidence: 99%

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Titration of chiral kink sites on Cu(643) using iodine adsorption

Kamakoti¹,

Horvath²,

Gellman³

et al. 2004

Surface Science

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“…Iodine adsorption on Cu (1 1 1) and Cu(1 0 0) LEED [8,9] and STM studies [10] have reported the formation of a ð ffiffi ffi…”

Section: Methodsmentioning

confidence: 99%

“…The adsorption of atomic iodine on Cu(1 1 1) and Cu(1 0 0) has been studied in a number of previous experiments [7][8][9][10][11][12][13][14]. We discuss the details of these previous studies below by comparing the results of our DFT calculations with the experimental observations.…”

Section: Introductionmentioning

confidence: 96%

Titration of chiral kink sites on Cu(643) using iodine adsorption

Kamakoti¹,

Horvath²,

Gellman³

et al. 2004

Surface Science

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“…This surface exposes four high symmetry binding sites for adsorption: on-top, bridging, and the fcc and hcp threefold hollow sites. Iodine is known to adsorb in the fcc sites and to form a ð ffiffi ffi 3 p Â ffiffi ffi 3 p ÞR30°ordered overlayer at a coverage of 0.33 monolayers (ML) [6][7][8]. The Cu(2 2 1) surface consists of (1 1 1) terraces separated by straight step edges with (1 1 0) structure ( Fig.…”

Section: Comparison Of Co Adsorption On Low and High Miller Index Pt mentioning

confidence: 99%

“…In Ref. [7], iodine was adsorbed on the surface by applying KI solutions to the Cu surface electrochemically. In Ref.…”

Section: Ethyl Iodide On Cu(1 1 1)mentioning

confidence: 99%

Ethyl iodide decomposition on Cu(111) and Cu(221)

Sung

Gellman

2004

Surface Science

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Ethyl iodide decomposition on the Cu(1 1 1) and Cu(2 2 1) surfaces has been studied using thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. On both surfaces ethyl iodide decomposes to produce ethyl groups and adsorbed iodine atoms. The ethyl groups decompose by b-hydride elimination to desorb as ethylene leaving adsorbed iodine atoms. The kinetics of b-hydride elimination on the Cu(2 2 1) surface are similar to those on the Cu(1 1 0) surface suggesting that the ethyl groups are reacting at the (1 1 0) step edges rather than on the (1 1 1) terraces. Vibrational spectra of the iodine atoms remaining on the surfaces after decomposition of the ethyl groups have been used to probe the iodine binding sites and to corroborate predictions based on density functional theory that the iodine atoms bind to the tops of the step edges. Iodine atoms on Cu(1 1 1) exhibit vibrational modes at 130 and 235 cm À1 that we assign empirically to in-plane and out-of-plane vibrations, respectively, of iodine atoms adsorbed at fcc sites on the (1 1 1) plane. On the stepped Cu(2 2 1) surface an additional peak appears at 80 cm À1 arising from iodine adsorbed at the step edges. The fact that this mode is at a lower frequency than the in-plane mode on the Cu(1 1 1) surface suggests that the iodine atom is adsorbed at the top of the step edge where its motion is unconstrained. These experimental results are consistent with the theoretical prediction that iodine atoms adsorb at the top of the step edges on the Cu(2 2 1) surface.

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“…25 -27 The XPS studies of monolayer coverages of iodine on Pd emersed from aqueous solution indicate that iodine is in a zerovalent state. 24 In situ scanning tunneling microscopy (STM) studies 25 of halide adsorption on Cu(111) indicate that adsorbed species have radii appropriate to zero-valent oxidation states. Chlorine adsorbed on Ag surfaces acts as a siteblocker to H 2 O dissociation under ultrahigh vacuum (UHV) conditions, 26 which suggests a similar zero-valent state.…”

Section: Introductionmentioning

confidence: 99%

Adsorbate‐catalyzed anodic dissolution and oxidation at surfaces in aqueous solutions

Kelber

Seshadri

2001

Surface & Interface Analysis

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Certain adsorbates, particularly sulfur and iodine, present at submonolayer coverages catalyze anodic dissolution or oxidation at selected transition metal surfaces. No change in adsorbate surface coverage or oxidation state is observed during the dissolution process, indicating that the process is truly catalyzed by the adsorbed impurity. This allows enhanced dissolution to take place in environments entirely free of solvated forms of the impurity. In the case of iodine, the mechanism depends in part on the relative strength of iodine-metal vs. metal-metal bond strengths, but also depends on other factors that are as yet poorly understood. In the case of adsorbed sulfur, the effect is related to the ability of adsorbed sulfur to hinder the formation of an oxide layer via the complete dissociation of water at the solid surface. The relevance of these adsorbate-catalyzed processes to intergranular stress corrosion cracking and semiconductor device processing are discussed.

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Adlayer Structures of Chlorine, Bromine, and Iodine on Cu(111) Electrode in Solution: In-Situ STM and ex-Situ LEED Studies

Cited by 84 publications

References 32 publications

Titration of chiral kink sites on Cu(643) using iodine adsorption

Titration of chiral kink sites on Cu(643) using iodine adsorption

Ethyl iodide decomposition on Cu(111) and Cu(221)

Adsorbate‐catalyzed anodic dissolution and oxidation at surfaces in aqueous solutions

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