Atomic Structure of Adsorbed Sulfate on Rh(111) in Sulfuric Acid Solution

Wan, Li; Yau, Shueh Lin; Itaya, Kingo

doi:10.1021/j100023a031

Cited by 203 publications

(198 citation statements)

References 12 publications

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“…The observed features on the Au(111) surface shown in Fig. 1b are very similar to those for the adsorbed sulfate/hydrogensulfate on Pt(111), 58 Rh(111), 59 Ir(111), 60 Pd(111), 61 and Cu(111).…”

Section: -57supporting

confidence: 63%

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Yoshimoto

2006

Bulletin of the Chemical Society of Japan

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In this research, molecular assembly and function of aromatic thiols, porphyrins, phthalocyanines, and fullerenes on gold single crystal surfaces was studied by electrochemical methods and scanning tunneling microscopy (STM). Surface functions of promoter molecules such as pyridinethiols, pyrimidinethiols, and benzenethiol for cytochrome c electrochemistry were characterized by electrochemical techniques. Adlayer structures of those molecules were investigated by in situ STM, and molecular orientations for each molecule on the Au surfaces were clarified at molecular level. Adlayers of porphyrins and phthalocyanines for electrocatalytic reduction of dioxygen were examined to elucidate the relationship between activity and adlayer structure. Stable two-dimensional arrays of cobalt porphyrins indicated two-electron reduction of O 2 to H 2 O 2 , whereas two-step four-electron reduction of O 2 to H 2 O occurred because of highly mobile porphyrinatoiron molecules on the surface. Furthermore, well-defined adlayers of crown-substituted phthalocyanine for host-guest interface and binary array consisting of porphyrin and phthalocyanine for the design of supramolecular nanoarchitectures were clearly visualized by STM. Finally, a unique approach for controlling molecular orientation was found by the formation of supramolecular assemblies consisting of porphyrin and fullerene. The electrochemical redox reaction of carbonyl and ferrocene moieties was promoted by using the simple method for the construction of a 1:1 supramolecular assembled film consisting of C 60 derivative and octaethylporphyrinatometal on Au single crystal surfaces.In the field of electrochemistry, surface modification is often used for controlling electron-transfer reactions and catalytic activity. Especially, the electron-transfer reaction of a metalloprotein is currently one of the most active areas in bioelectrochemistry and related fields.

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Section: -57supporting

confidence: 63%

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Yoshimoto

2006

Bulletin of the Chemical Society of Japan

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“…These bands are in good agreement with those reported for sulfate adsorbed on Rh(111) in sulfuric acid solutions 16 . As already discussed in previous publications 6 , the positive feature at 1100 cm -1 is due to the dissolved SO 4 2-, which presents only one active stretching vibration located at this wavenumber. The two negative features correspond to the S-O stretching vibrations of adsorbed sulfate.…”

Section: Effect Of Solution Aciditysupporting

confidence: 67%

“…The spectra of adsorbed sulfate at pH 3 and 0.2 at the maximum coverage, where SO 4 2-and HSO 4 -predominate, respectively 18 are shown for Rh(111) ( Figure 1) and for Rh(100) (Figure 2). For the sulfate adsorbed from a solution containing SO 4 2-ions, three bands can be clearly distinguished ( Figure 1a).…”

Section: Effect Of Solution Aciditymentioning

confidence: 99%

“…For the sulfate adsorbed from a solution containing SO 4 2-ions, three bands can be clearly distinguished ( Figure 1a). One positive-going band is centered at 1100 cm -1 and two negative-going bands are located at 1247 cm -1 and 960 cm -1 .…”

Section: Effect Of Solution Aciditymentioning

confidence: 99%

“…The adsorption of sulfate and other oxyanions experimented a renewed interest with the introduction of auxiliary techniques in electrochemistry, such as in situ FTIR spectroscopy 1 , radioactive labeling 2 and in situ scanning tunneling microscopy (STM) [3][4][5] .…”

Section: Introductionmentioning

confidence: 99%

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On the adsorption of sulfate on low Miller index Rh(hkl) electrodes: an in situ vibrational analysis

Moraes¹,

Nart²

2001

J. Braz. Chem. Soc.

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A adsorção de íon sulfato em eletrodos de Rh(111), Rh(100) e Rh(110) foi estudada utilizandose a técnica de espectroscopia de FTIR por reflectância in situ. Foi observada somente uma banda vibracional localizada acima de 1200 cm -1 para as três superfícies com baixo índice de Miller e uma banda fraca em 960 cm -1 para o sulfato adsorvido em Rh(111). A banda forte acima de 1200 cm -1 é dependente do potencial com uma variação de 50 cm -1 V -1 . Não foram observadas diferenças espectrais ao se variar a acidez da solução de forma a gerar soluções contendo sulfato ou sulfato ácido. Este resultado é interpretado em termos de uma dissociação completa dos íons, produzindo somente SO 4 2-adsorvido. A orientação da superfície afeta somente a quantidade de espécies sulfato adsorvidas. Parece que o mesmo tipo de adsorbato é encontrado em Rh(111), Rh(110) e Rh(100).The adsorption of sulfate ion on Rh(111), Rh(100) and Rh(110) electrodes was studied using in situ FTIR reflection spectroscopy. For wavenumbers above 1200 cm -1 , only one strong vibrational band is observed for adsorbed sulfate on the three low index rhodium surfaces. A weak band at 960 cm -1 is also observed for Rh(111). The strong band above 1200 cm -1 is potential dependent with a tuning rate of 50 cm -1 V -1 . No differences were observed upon changing the solution acidity in order to provide sulfate or bisulfate in solution. This result is interpreted in terms of complete dissociation of the ions, giving only adsorbed SO 4 2-. The surface orientation affects only the amount of the adsorbed sulfate species. It seems that the same adsorbed sulfate is present on Rh(111), Rh(110) and Rh(100).

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In-situ Characterization of Metal/Electrolyte Interfaces: Sulfate Adsorption on Cu(111)

Arenz

Broekmann

Lennartz

et al. 2001

phys. stat. sol. (a)

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As a prototypical example of a metal-electrolyte interface the adsorption of sulfate on well defined Cu(111) single crystal electrodes from a 5 mM H 2 SO 4 solution has been studied by means of in-situ electrochemical scanning tunneling microscopy (EC-STM) and infrared reflection absorption spectroscopy (IRAS). The EC-STM images show the formation of the well-known Moiré -like structure upon adsorption of sulfate on the Cu(111) surface. While IR frequency data fail to provide information about the anion adsorption site, high-resolution STM images taken under specific tunneling conditions also clearly reveal the C 2v symmetry and the twofold bridging coordination of the sulfate adsorption complex. Analysis of the IR intensities, however, does show that the sulfate adsorption starts at a potential noticeably lower (less anodic) than the potential of first Moiré formation. In this potential region the adsorbed sulfate is very mobile on the surface and difficult to image by STM. Adsorption rate and sulfate coverage are strongly dependent on the electrode potential. The slow adsorption process leading to a well ordered Moiré structure is compared to a fast adsorption process by applying potential steps. Under the latter conditions no or only barely ordered sulfate adlayers are observed with STM. As shown by the IR measurements, however, the saturation coverage is hardly affected by the adsorption rate.

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Atomic Structure of Adsorbed Sulfate on Rh(111) in Sulfuric Acid Solution

Cited by 203 publications

References 12 publications

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

Molecular Assemblies of Functional Molecules on Gold Electrode Surfaces Studied by Electrochemical Scanning Tunneling Microscopy: Relationship between Function and Adlayer Structures

On the adsorption of sulfate on low Miller index Rh(hkl) electrodes: an in situ vibrational analysis

In-situ Characterization of Metal/Electrolyte Interfaces: Sulfate Adsorption on Cu(111)

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