Thermodynamic analysis of (bi)sulphate adsorption on a Pt(111) electrode as a function of pH

Garcı́a-Aráez, Nuria; Climent, Vı́ctor; Rodríguez, Paramaconi; Feliu, Juan M.

doi:10.1016/j.electacta.2007.12.086

Cited by 67 publications

(88 citation statements)

References 29 publications

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“…This fact clearly indicates that the adsorption of anions is disfavored as the temperature increases. The second feature, the small bump at 0.6-0.7 is related the completion of the sulfate layer [32]. In this case, this process is more reversible with the temperature, as the peak separation between positive and negative scan direction diminishes, but there is no significant peak shift.…”

Section: Temperature Effects On the Behavior Of The Electrodes In Thementioning

confidence: 93%

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On the activation energy of the formic acid oxidation reaction on platinum electrodes

Perales-Rondón

Herrero

Feliu

2015

Journal of Electroanalytical Chemistry

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Abstract.A temperature dependent study on the formic acid oxidation reaction has been carried out in order to determine the activation energy of this reaction on different platinum single crystal electrodes, namely Pt(100), Pt(111), Pt(554) and Pt (544) (100) electrode, and the activation values for this process range between 20 and 100 kJ/mol. These results have been explained using a reaction mechanism in which the oxidation of formic acid requires the presence of a pre-adsorbed anion on the electrode surface.

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Section: Temperature Effects On the Behavior Of The Electrodes In Thementioning

confidence: 93%

“…For the Pt(100) and Pt(111) electrodes, achieving a long range order in the sulfate adlayer is the key factor for the completion of the anion layer [32]. As aforementioned, the small bump between 0.6-0.7 V for the Pt(111) electrode is related to the completion of the adalyer.…”

Section: Temperature Effects On the Behavior Of The Electrodes In Thementioning

confidence: 99%

On the activation energy of the formic acid oxidation reaction on platinum electrodes

Perales-Rondón

Herrero

Feliu

2015

Journal of Electroanalytical Chemistry

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“…(1 ) 1 In the particular case where z=-1 equation (17) reduces to: 8,53 indicating that these anions are not completely discharged in the adsorbed state. The low slope values mentioned above indicate that the description of the deprotonation in equation (13) as whole electron transfer process might not be accurate and the process would be better described as just a partial reorganization of charges at the interphase as a consequence of the deprotonation.…”

Section: Methodsmentioning

confidence: 99%

“…7,15 Thermodynamic analysis allowed the determination of parameters associated to this process, such as charge transfer numbers and energies of adsorption. 6,8,[16][17][18] When the study includes a surface acid base equilibrium, pH variation allows discrimination of the nature of the adsorbed species. 4,19 In this way, it was demonstrated that Pt(111) in contact with sulphuric acid solutions led to sulphate adsorption, 19 in agreement with results from other experimental techniques.…”

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confidence: 99%

Surface Acid–Base Properties of Anion-Adsorbed Species at Pt(111) Electrode Surfaces in Contact with CO₂-Containing Perchloric Acid Solutions

et al. 2016

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Abstract:Carbonate and bicarbonate adsorption on Pt(111) electrodes from CO 2 saturated acidic solutions is investigated by cyclic voltammetry and Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS). Spectroscopic results show carbonate and bicarbonate adsorption even at pH=1, where bulk concentration of these anions is negligible. Moreover, analysis of the potential dependence of band intensities corresponding to adsorbed carbonate and bicarbonate reveals an effect of the electrode potential on the surface acid-base equilibrium. In this regards, increasing potentials favor bicarbonate deprotonation, leading to carbonate formation. A tentative thermodynamic analysis is given to rationalize these trends.

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“…However the spike potential decreases with increasing sulphate concentration, as expected for a sulphate adsorption/desorption process, and it is observed for the bare Pt (111) surface. [28][29][30] Others species that could potentially contribute to the voltammogram of thallium modified Pt (111) are hydrogen and OH adsorption. These processes can be studied by analysing the effect of pH on the voltammograms.…”

Section: Methodsmentioning

confidence: 99%

New insight on the behavior of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes

Rodríguez

Garcı́a-Aráez

Herrero

et al. 2015

Electrochimica Acta

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Please cite this article as: P.Rodriguez, N.García-Aráez, E.Herrero, J.M.Feliu, New insight on the behaviour of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes, Electrochimica Acta http://dx.doi.org/10.1016/j.electacta. 2014.11.019 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. 1New insight on the behaviour of the irreversible adsorption and underpotential deposition of thallium on platinum (111) AbstractWe report, for the first time, the electrochemical behaviour of thallium irreversibly adsorbed on Pt (111) and platinum stepped surfaces composed of (111) terraces and monoatomic steps. Similar to the case of thallium UPD, the voltammograms obtained after thallium irreversible adsorption present three characteristic features. After a careful analysis of the effect of the thallium concentration, the concentration and nature of the anion of the supporting electrolyte and the pH of the solution on these voltammetric features, we have been able to ascribe these processes to Tl/Tl + oxidation and anion adsorption on the Tlmodified surface. In addition, the results obtained with stepped surfaces, indicate that some of the features are clearly associated to the presence of (111) surface domains, and thus they could be used for the quantification of these sites.

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Thermodynamic analysis of (bi)sulphate adsorption on a Pt(111) electrode as a function of pH

Cited by 67 publications

References 29 publications

On the activation energy of the formic acid oxidation reaction on platinum electrodes

On the activation energy of the formic acid oxidation reaction on platinum electrodes

Surface Acid–Base Properties of Anion-Adsorbed Species at Pt(111) Electrode Surfaces in Contact with CO₂-Containing Perchloric Acid Solutions

New insight on the behavior of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes

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Thermodynamic analysis of (bi)sulphate adsorption on a Pt(111) electrode as a function of pH

Cited by 67 publications

References 29 publications

On the activation energy of the formic acid oxidation reaction on platinum electrodes

On the activation energy of the formic acid oxidation reaction on platinum electrodes

Surface Acid–Base Properties of Anion-Adsorbed Species at Pt(111) Electrode Surfaces in Contact with CO2-Containing Perchloric Acid Solutions

New insight on the behavior of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes

Contact Info

Product

Resources

About

Surface Acid–Base Properties of Anion-Adsorbed Species at Pt(111) Electrode Surfaces in Contact with CO₂-Containing Perchloric Acid Solutions