Adsorption of sulfate ions on monocrystalline copper electrodes: the structural effects

Smoliński, Sławomir; Sobkowski, Jerzy

doi:10.1016/s0022-0728(98)00424-0

Cited by 24 publications

(20 citation statements)

References 21 publications

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“…[30,31] For the Cu(111) surface radiotracer experiments yielded a maximum sulphate coverage of the order of 0.2 ML, referenced to the topmost Cu layer. [13] The absolute surface excess of sulphate corresponded well with that in the Cu (1 1) UPD structure on Au(111) and was slightly lower than the sulphate surface excess in the Cu ( ffiffi ffi 3 p Â ffiffi ffi 3 p ) UPD on Au(111). [9] Hence, from these data on well-ordered surfaces, additional sulphate adsorption upon the first stages of bulk Cu deposition on Cu UPD is not expected to occur on well-ordered Au(111).…”

Section: à2mentioning

confidence: 59%

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Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

2010

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Heat effects upon Cu deposition on polycrystalline Au surfaces from sulphuric acid electrolytes were calorimetrically measured. By combination of pyroelectric temperature detection at the backside of a thin electrode foil with pulsed electrochemistry, sensitivities to electrochemical conversions of a few percent of a Cu monolayer (ML), corresponding to about 1 microJ cm(-2) were achieved. We compared the heat evolution upon Cu under potential deposition (UPD), Cu deposition onto a fully developed Cu UPD layer and bulk Cu deposition onto a 300 ML thick Cu layer on Au. The heat effects were measured dependent on the amplitudes of the applied potential steps, that is, the driving forces of the respective reactions. From the differences of the heat effects among the Cu deposition processes, we deduced implications on the reaction mechanisms. For Cu UPD, the heat effects were explicable by the deposition of 1.3 Cu atoms per two electrons flowing to the electrode accompanied by sulphate coadsorption, similar to Cu UPD from sulphuric acid solutions on Au(111). Upon Cu deposition on a Cu UPD layer the heat effects signal considerable anion coadsorption up to the deposition of about 0.5 ML of Cu. At higher conversions the deposition mechanism gradually changes towards bulk Cu deposition, accompanied by reduction of the sulphate coverage.

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Section: à2mentioning

confidence: 59%

“…[10,11] Radio-tracer studies proved the presence of sulphate on Cu UPD and Cu surfaces. [12][13][14] For more detailed information on Cu underpotential deposition see, for example, refs. [9,15] and a recent review.…”

Section: Introductionmentioning

confidence: 99%

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

2010

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“…It is conceivable that the sulfate coverage on the Cu (1 × 1) UPD layer is lower than on the (√3 × √3) UPD I structure, since the adsorption state of sulfate on the (1 × 1) Cu layer strongly differs from that in the (√3 × √3) structure, where sulfate was found to be adsorbed in the hollow sites of a Cu honeycomb structure. 2 For Cu(111) a maximum sulfate coverage of about 0.2 ML was deduced from STM and radiotracer measurements, 64,65 which is considerably less than the sulfate coverage in the (√3 × √3) Cu UPD layer on Au(111). Hence, upon the completion of the (1 × 1) Cu layer a diminishment of the sulfate coverage is anticipated.…”

mentioning

confidence: 99%

Role of Anions During the Cu Underpotential Deposition on Au(111): A Microcalorimetric Investigation

Frittmann

Schuster

2016

J. Phys. Chem. C

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We measured the molar Peltier heat during the course of Cu underpotential deposition (UPD) in sulfate-containing solutions by electrochemical microcalorimetry. The molar Peltier heat during Cu UPD deviates considerably from that of Cu bulk deposition in the corresponding solution. Since the molar Peltier heat directly reflects the reaction entropy of the involved electrochemical reaction, including also charge-neutral side processes, this finding signals significant contributions of non-Faradaic side reactions. For the first stage of the Cu UPD this process is known to be coadsorption of Cu2+ and sulfate species. We retrieved the potential dependent surface coverages of Cu and sulfate during the first Cu UPD stage with the single additional assumption that the Cu coverage in the first stage of the Cu UPD reaches 2/3 ML. In addition, we found that both HSO4(ad) and SO4(ad) are adsorbed on the surface with a noticeable surplus of bisulfate. For the second stage of Cu UPD, i.e., the completion of the first (1 × 1) Cu monolayer, our data indicates a charge-neutral side process, which cannot be inferred from the current potential relationship as measured, e.g., by cyclic voltammetry. This side process has considerably high positive reaction entropy and is present also for Cu UPD in perchlorate solutions. We interpret this side process as substitution of adsorbed sulfate or perchlorate anions by oxygen species upon completion of the first Cu monolayer, whereby the potential of zero charge shifts negatively.

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“…However, it has been reported that only sulfate anions adsorb to the Cu surface , whereas alkali metal cations do not have substantial influences in the solution containing sulfate anions . Though sulfate anions could adsorb to Cu surface, the gas evolution reaction could only be affected in the presence of Cu (100) surface . In this research, a polycrystalline Cu catalyst was used to the electrochemical reduction of N 2 O and the onset potential of N 2 O reduction in both K 2 SO 4 (−0.8 V) and Na 2 SO 4 (−0.7 V) did not change in the concentration region we have investigated.…”

Section: Resultsmentioning

confidence: 87%

“…In this research, Na + , K + cations and SO 4 2− anion could bring about these adsorption effects. However, it has been reported that only sulfate anions adsorb to the Cu surface , whereas alkali metal cations do not have substantial influences in the solution containing sulfate anions . Though sulfate anions could adsorb to Cu surface, the gas evolution reaction could only be affected in the presence of Cu (100) surface .…”

Section: Resultsmentioning

confidence: 99%

Optimization of Solution Condition for an Effective Electrochemical Reduction of N₂O

et al. 2019

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An effective electrochemical reduction of nitrous oxide (N2O) is established by controlling solution compositions in this study. N2O was electrochemically reduced varying solvent composition and supporting electrolytes (K2SO4 and Na2SO4) concentrations. The differences in reduction current density and solution resistance were analyzed via linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS), respectively, depending on solution conditions. UV‐Vis spectroscopy was adopted to measure the solubility of N2O. As a result, among the conditions investigated in this study, 300 mM of K2SO4 and aqueous based solution were revealed as an optimum condition for the electrochemical N2O reduction. At 300 mM of K2SO4, the highest current density was obtained due to a high conductance of the electrolyte and a moderate solubility of N2O.

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Adsorption of sulfate ions on monocrystalline copper electrodes: the structural effects

Cited by 24 publications

References 21 publications

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

Role of Anions During the Cu Underpotential Deposition on Au(111): A Microcalorimetric Investigation

Optimization of Solution Condition for an Effective Electrochemical Reduction of N₂O

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Adsorption of sulfate ions on monocrystalline copper electrodes: the structural effects

Cited by 24 publications

References 21 publications

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold

Role of Anions During the Cu Underpotential Deposition on Au(111): A Microcalorimetric Investigation

Optimization of Solution Condition for an Effective Electrochemical Reduction of N2O

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Optimization of Solution Condition for an Effective Electrochemical Reduction of N₂O