An SFG investigation of Au(111) and Au(210) electrodes in aqueous solutions containing KCN and cetylpyridinium chloride

Bozzini, Benedetto; Mele, Claudio; Fanigliulo, Ameriga; Busson, Bertrand; Vidal, Frank; Tadjeddine, A.

doi:10.1016/j.jelechem.2004.08.003

Cited by 31 publications

(36 citation statements)

References 38 publications

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“…Quantitative effects of 4CP addition emerge only for Au(111). A similar effect was noticed for cetylpyridinium chloride [23]: closely-packed surfaces, such as (111) for fcc Au, are affected (i.e. the desorption rate is increased), while loosely packed-such as (210)-and defective onessuch as that of a polycrystal-exhibit the same desorption rate as in the absence of the additive.…”

Section: 11)supporting

confidence: 61%

“…The more open face exhibits a lower activity towards both anodic and cathodic 4CP decomposition, while the more packed one displays an enhanced cathodic activity and a reduced anodic one. As observed in [23,27], a more open face corresponds to enhanced metal-CN -interaction. These conditions seem to correlate with a lower electrodic activity towards 4CP decomposition.…”

Section: Cyclic Voltammetrysupporting

confidence: 52%

“…The coadsorption of benzyldimethylphenylammonium chloride and CN -was studied during Au electrodeposition [22]. Recent work in our group has attacked the problem of the coadsorption of CN -and cetylpyridinium chloride (CPC) onto Au(111) and Au(210) by SFG [23] and onto Ag(111) by FT-IR and SERS [24]. Two basic modes of coadsorption of CN -and organics were found.…”

Section: Introductionmentioning

confidence: 99%

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SFG and DFG investigation of Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

et al. 2008

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We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au (210), polycrystalline Au, Au-Cu and Au-Ag-Cu electrodes in contact with aqueous solutions containing CN -and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN -and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN -electrolyte, denote changes in the CN -adsorption characteristics and effects of the adsorbed CN -layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN -. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN -monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.

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Section: 11)supporting

confidence: 61%

Section: Cyclic Voltammetrysupporting

confidence: 52%

Section: Introductionmentioning

confidence: 99%

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SFG and DFG investigation of Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

et al. 2008

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“…For the solution containing PEG and Cl À ; b c is still higher; this can be interpreted as due to an increase of resistance to electron transfer due to the mode of adsorption of Cl ) , which is expected to be positioned between PEG and metal surface [30]. In the presence of Cl ) , on increasing the rotation rate, the values of j 0 and b c change from those characteristic for PEG-containing solutions towards those for PEG-free solutions.…”

Section: Resultsmentioning

confidence: 93%

Electrodeposition of Cu from Acidic Sulphate Solutions in the Presence of PEG: An Electrochemical and Spectroelectrochemical Investigation – Part I

et al. 2006

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This paper deals with the effects of PEG during Cu electrodeposition from an acidic sulphate solution. This investigation was carried out with electrochemical and spectroelectrochemical techniques. Potentiostatically grown layers were examined by scanning electron microscopy. Adsorption of PEG on the growing Cu surface can be inferred from electrokinetic, SERS and morphological evidence: variations of the estimated exchange current density, qualitative and quantitative differences in the potentiostatic transients, changes on the cathodic current efficiency, effects on the three-dimensional crystallisation mode under both compact and dendritic growth conditions, appearance of surface-enhanced PEG-related Raman bands. SERS spectra revealed cathodic reactivity of adsorbed PEG.

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“…The CN¯ stretching bands exhibit a parabolic potential dependence (see Figure 5, for theoretical details on this point, see 32 16,21 . As far as isotopic effects and extramolecular vibrations are concerned, the same comments as in Section 3.1.…”

Section: Au Electrodeposition From Au(cn) 2¯ and Au(cn) 4¯ Solutionsmentioning

confidence: 98%

A SERS Investigation of Cyanide Adsorption and Reactivity during the Electrodeposition of Gold, Silver, and Copper from Aqueous Cyanocomplexes Solutions

et al. 2008

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In this paper we report on the reactivity of adsorbed cyanide deriving from ligand release during metal electrodeposition from cyanocomplex solutions of Au(I), Au(III), Ag(I) and Cu(I) in H 2 O and D 2 O. When CN¯ is adsorbed at cathodic potentials in excess of the HER threshold, metal-dependent reactivity can be detected by SERS. Finite surface coverages with adsorbed CN¯ at such cathodic potentials can be obtained only if CN¯ is delivered directly to the cathode surface as by decomplexing of the cyanocomplexes of the metals undergoing cathodic reduction. In Au(I) and Au(III) baths, Au-CN¯ reacts with Au-H• and is hydrogenated to adsorbed CH 2 =NH and CH 3 -NH 2 .In Ag(I) baths, Ag-CN¯ reacts with Ag-H • giving rise to polycyanogens. No reactivity of Cu-CN¯ was found, under otherwise identical conditions. Our conclusions are supported also by dedicated DFT molecular computations.

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An SFG investigation of Au(111) and Au(210) electrodes in aqueous solutions containing KCN and cetylpyridinium chloride

Cited by 31 publications

References 38 publications

SFG and DFG investigation of Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

SFG and DFG investigation of Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

Electrodeposition of Cu from Acidic Sulphate Solutions in the Presence of PEG: An Electrochemical and Spectroelectrochemical Investigation – Part I

A SERS Investigation of Cyanide Adsorption and Reactivity during the Electrodeposition of Gold, Silver, and Copper from Aqueous Cyanocomplexes Solutions

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