AFM observation of a sulfate adlayer on Au(111) in sulfuric acid solution

Nishizawa, Takashi; Nakada, T.; Kinoshita, Yukinori; Miyashita, Satoru; Sazaki, Gen; Komatsu, Hideyuki

doi:10.1016/s0039-6028(96)01091-6

Cited by 23 publications

(17 citation statements)

References 15 publications

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“…They are also important for controlling the performance of the electrodes in a wide variety of electrochemical devices such as solar cells, batteries and sensors. Ion adsorption on electrodes has been regarded as a major factor that controls the surface potentials and charge density and has been studied using many sensitive analytical methods such as surface X-ray scattering (SXS), − electrochemical scanning tunneling microscopy (EC-STM), , atomic force microscopy (EC-AFM), electrochemical quartz microbalance (EQCM), , infrared spectroscopy, and sum frequency generation spectroscopy (SFG) . However, these methods mostly provide only qualitative information.…”

Section: Introductionmentioning

confidence: 99%

Anion Adsorption on Gold Electrodes Studied by Electrochemical Surface Forces Measurement

Kasuya¹,

Tsukasa²,

Masuda

et al. 2016

J. Phys. Chem. C

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The adsorption of ions on electrodes determines the surface potential and charge density of the electrode, thus, quantitative evaluation of the ion adsorption on an electrode is necessary and has been one of the central questions in electrochemistry. Electrochemical Surface Forces Apparatus (EC-SFA) can provide an efficient characterization method of these properties. The interactions between two gold electrodes in various electrolyte solutions, that is, 1 mM aqueous KClO 4 , K 2 SO 4 , and KCl, were measured by controlling of the electrochemical potential (E). The longrange, double layer repulsion and the jump-in due to the van der Waals attraction at the surface separation of about 20 nm were observed between the electrodes in all the solutions. We evaluated the ψ 0 and σ values employing DLVO fitting of these interactions. The signs of ψ 0 and σ were determined from the interaction between the electrode and negatively charged mica surfaces. This study demonstrated that the σ values were negative and similar in all the solutions when the applied potential E was lower than the potential of zero charge (pzc). When the potential E was increased to near the pzc, the σ values were negative and low and in the order of KClO 4 ≈ K 2 SO 4 > KCl. When the potential E was further increased to the pzc, the σ value was positive in aqueous KClO 4 because of less anion adsorption on the gold electrode, while those in the K 2 SO 4 and KCl aqueous solutions were negative due to higher adsorption amount of the anions. The method demonstrated in this study enabled us to quantitatively evaluate the influences of the ion adsorption on the effective surface potential and charge density of the electrodes, which should determine the performances of electrochemical devices.

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Section: Introductionmentioning

confidence: 99%

Anion Adsorption on Gold Electrodes Studied by Electrochemical Surface Forces Measurement

Kasuya¹,

Tsukasa²,

Masuda

et al. 2016

J. Phys. Chem. C

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“…Due to its importance in the chemistry and physics of interfaces the UPD phenomena has been studied extensively by traditional electrochemical methods such as cyclic voltammetry [10,36], rotating ring disk measurements [37] and chronocoulometry [38]. Recently in-situ techniques have been used such as Scanning Tunnelling Microscope (STM) [8,14,17,18,39], Atomic Force Microscopy (AFM) [21,40,41], X-ray techniques and also ex-situ techniques such as Low Energy Electron Diffraction (LEED), RHEED and AES [1,42,43].…”

Section: Introductionmentioning

confidence: 99%

A reflectance anisotropy spectroscopy study of underpotential deposition of copper onto Au(110)

Farell

Lucas

et al. 2005

Physica Status Solidi (b)

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The underpotential deposition of Cu on Au(110) has been monitored by Reflection Anisotropy Spectroscopy (RAS). The changes in the intensity of spectral features observed at 2.6 eV and 3.4 eV in the RA spectrum of Au (110) that are induced by the deposition of Cu occur on different timescales. It is suggested that these changes arise, respectively, from the partial quenching of surface states and from changes in surface morphology.

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“…Peak D1 indicates the lifting of the reconstruction of gold caused by the adsorption of sulfate. , Shi et al assign the point of zero charge (pzc) to the left side of the tall D1 peak ( E (pzc) ≈ 0.18 V SCE ), where the anion coverage is about zero . At potentials more positive than D1, there is a broad shoulder D2, which corresponds to a medium coverage by mobile anions. ,,, The phase transition to an ordered sulfate overlayer with a (√3 × √7) structure occurs at about 0.78 V SCE , resulting in peak D3. , It should be noted that the height of the D3 peak is crucially dependent on the long-range order of the (111) terraces. Although with our sample, the height of this peak is comparable to literature data on single-crystalline Au(111) surfaces, higher D3 peaks were observed for very well-ordered surfaces. ,, For a discussion on the influence of surface misorientation on the CV peaks, see ref .…”

Section: Resultsmentioning

confidence: 99%

“…8 At potentials more positive than D1, there is a broad shoulder D2, which corresponds to a medium coverage by mobile anions. 9,11,15,44 The phase transition to an ordered sulfate overlayer with a (√3 × √7) structure occurs at about 0.78 V SCE , resulting in peak D3. 11,12 It should be noted that the height of the D3 peak is crucially dependent on the long-range order of the (111) terraces.…”

Section: Cyclic Voltammogram (Cv)mentioning

confidence: 99%

Unraveling Compositional Changes of the Double Layer upon Sulfate Adsorption on Au(111) by Surface Plasmon Resonance

et al. 2019

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The potential-induced sulfate adsorption on (111)-textured Au films in 0.1 M sulfuric acid was studied by surface plasmon resonance (SPR) measurements. Full SPR curves were recorded with millisecond time resolution allowing for simultaneous measurement of SPR and cyclic voltammetry data. We could quantitatively account for the observed SPR shift within a five-phase model, which includes the effects of electron depletion in the topmost electrode layer upon positive polarization. From the refractive index change in the modeled sulfate layer and the sulfate surface excess, as known from the literature, we derived an effective polarizability of αeff = 3.9 Å3 per sulfate species entering the adlayer from the bulk of the solution. Since this value comes close to that of sulfate ions in solution, no significant side processes like exchange of water between the adlayer and the solution are expected. This directly implies compression of the adlayer species upon positive polarization of the electrode and hence a negative reaction volume for the sulfate layer formation process, signaling strong electrostriction of water in the adlayer.

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AFM observation of a sulfate adlayer on Au(111) in sulfuric acid solution

Cited by 23 publications

References 15 publications

Anion Adsorption on Gold Electrodes Studied by Electrochemical Surface Forces Measurement

Anion Adsorption on Gold Electrodes Studied by Electrochemical Surface Forces Measurement

A reflectance anisotropy spectroscopy study of underpotential deposition of copper onto Au(110)

Unraveling Compositional Changes of the Double Layer upon Sulfate Adsorption on Au(111) by Surface Plasmon Resonance

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