Erratum: Study of underpotentially deposited copper on gold by fluorescence detected surface EXAFS [J. Chem. Phys. <b>8</b>
                  <b>5</b>, 6732 (1986)]

Blum, Loı̈c J.; Abruña, H. D.; White, Jeffrey A.; Albarelli, M. J.; Gordon, Judith R.; Borges, Gary L.; Samant, Mahesh G.; Melroy, Owen R.

doi:10.1063/1.452790

Cited by 5 publications

(12 citation statements)

References 5 publications

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“…The location of the sulfur atoms with respect to the Cu-(1×1) surface deviates substantially from the atop position predicted via previous EXAFS measurements of the Cu(UPD)/Au(111) system in sulfate supporting electrolyte. 18,19 In fact, placing the sulfur atom directly above each Cu adatom represents a chemically unreasonable arrangement in which the oxygen atoms would need to be bonded to more than one sulfur atom and yields an inferior fit to the experimental EXAFS (R g 50%).…”

Section: Exafs Measurements: Cu Upd On Bare Au(111)mentioning

confidence: 99%

“…One of the most extensively investigated systems, Cu UPD on Au(111) from sulfate supporting electrolyte, – provides the initial focus of this work. The process of Cu UPD on Au(111) in the presence of sulfate counterions is known to occur in two distinct stages: In the first stage, the Cu adatoms occupy 3-fold hollow sites on the Au(111) substrate in a (√3×√3) R 30°) (surface coverage θ sc = 0.67) arrangement, which supports a coadsorbed (√3×√3) R 30° (θ sc = 0.33) overlayer of sulfate ions. – In the second stage, additional Cu is adsorbed under more reducing conditions to complete a commensurate Cu-(1 × 1) monolayer (θ sc = 1), in which the adatoms continue to reside in the 3-fold hollow sites on Au(111). ,, …”

Section: Introductionmentioning

confidence: 99%

“…10,13,14 The selection of this Cu(UPD)/Au(111) system is of particular significance because it has been studied previously using SXS/ XRD and XAS with varying degrees of success: SXS and XRD were successfully employed in assignment of the interfacial arrangement (described above) for the first stage of Cu UPD. 21,22 In contrast, XAS studies 18,19,[22][23][24][25]27,28 provide structures of the Cu adlayer and/or the coadsorbed overlayer of sulfate counterions that conflict both with one another and with the accepted model for Cu UPD from a sulfate supporting electrolyte. For example, Tadjeddine and co-workers [23][24][25] propose that the Cu adopts ( 3× 3)R30°(θ sc ) 0.33) and c(5×5) (θ sc ) 0.6) adlayer structures prior to formation of the Cu-(1×1) adlayer arrangement.…”

Section: Introductionmentioning

confidence: 99%

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X-ray Absorption Spectroscopy Characterization of Cu Underpotential Deposition on Au(111) and Organothiol-Self-Assembled-Monolayer-Modified Au(111) Electrodes from Sulfate Supporting Electrolyte

et al. 2009

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Cu K-edge X-ray absorption spectroscopy (XAS) has been used for the in situ structural characterization of Cu monolayers prepared on both bare Au(111) and butanethiol self-assembled monolayer (BT-SAM)-modified Au(111) electrodes by underpotential deposition (UPD) from a sulfate supporting electrolyte. In conjunction with electrochemical measurements, the XAS studies enable assignment of the evolution in interfacial structure of both systems as a function of the applied electrochemical potential. The measurements of Cu adlayer formation on unmodified Au(111) from sulfate supporting electrolyte, an extensively studied and model UPD system, allow a reevaluation of XAS as an alternative or complementary technique to more established methods for the structural investigation of the electrified interface, such as X-ray diffraction (XRD) and surface X-ray scattering (SXS). The experiments reported in this paper indicate that recent technological advances enable XAS studies of UPD monolayers to be conducted on a time scale comparable to that of XRD and SXS. Meanwhile, the XAS data are consistent with the accepted model for the evolution in structure of the Cu adlayer under increasingly reducing conditions: following the formation of a commensurate ( 3× 3)R30°( θ sc ) 0.67) adlayer in which the Cu adatoms occupy the 3-fold hollow sites, additional UPD results in a Cu-(1×1) monolayer structure. Theoretical modeling of the XAS data also allows a structural assignment for the coadsorbed anion overlayer and illustrates that the sulfate ions adopt a ( 3× 3)R30°(θ sc ) 0.33) arrangement on the surface of both Cu adlayers. The XAS characterization of Cu UPD on BT-SAM-modified Au electrodes indicates that the Cu adatoms reside in face-centered cubic 3-fold hollow sites of an unreconstructed Au(111) surface. This is significant because it suggests that formation of the Cu UPD adlayer lifts, at least in part, the organothiol-SAM-induced reconstruction of the Au substrate surface. The local environment of the Cu adatoms presents the possibility that adlayer regions with a Cu-(1×1) structure form on the Au surface, which support a coadsorbed ( 3× 3)R30°(θ sc ) 0.33) overlayer of BT sulfur atoms residing in the 3-fold hollow sites of the UPD monolayer.

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Section: Exafs Measurements: Cu Upd On Bare Au(111)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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X-ray Absorption Spectroscopy Characterization of Cu Underpotential Deposition on Au(111) and Organothiol-Self-Assembled-Monolayer-Modified Au(111) Electrodes from Sulfate Supporting Electrolyte

et al. 2009

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“…For example, the deposition of Cu on the Au(111) face forms two phases according to the deposition potential. These phases have been observed ex-situ [8] and in situ [5] [29] [30], [10]. [11].…”

Section: Phase Transitions At Electrode Surfacesmentioning

confidence: 99%

Phase transitions at liquid–solid interfaces: Padé approximant for adsorption isotherms and voltammograms

Blum

Huckaby

1991

The Journal of Chemical Physics

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“…A monolayer of copper was underpotentially deposited in situ at 130 mV vs Ag/AgCl on a gold electrode from a 2 x 10-5 M CuS04 solution containing 1 M H2S04 as a supporting electrolyte. 81 The gold electrode was prepared by epitaxially depositing Au(lll) onto a cleaved mica substrate. The X-ray spectrum of UPD copper was compared to spectra of aqueous CuS04 and CuAu alloy.…”

Section: Introductionmentioning

confidence: 99%

EXAFS spectroelectrochemistry

Sharpe¹,

Heineman²,

Elder³

1990

Chem. Rev.

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Erratum: Study of underpotentially deposited copper on gold by fluorescence detected surface EXAFS [J. Chem. Phys. 8 5, 6732 (1986)]

Cited by 5 publications

References 5 publications

X-ray Absorption Spectroscopy Characterization of Cu Underpotential Deposition on Au(111) and Organothiol-Self-Assembled-Monolayer-Modified Au(111) Electrodes from Sulfate Supporting Electrolyte

X-ray Absorption Spectroscopy Characterization of Cu Underpotential Deposition on Au(111) and Organothiol-Self-Assembled-Monolayer-Modified Au(111) Electrodes from Sulfate Supporting Electrolyte

Phase transitions at liquid–solid interfaces: Padé approximant for adsorption isotherms and voltammograms

EXAFS spectroelectrochemistry

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