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Elucidation of the chemical nature of adsorbed species for Pt(111) in H2SO4 solutions by thermodynamic analysis

Elucidation of the chemical nature of adsorbed species for Pt(111) in H2SO4 solutions by thermodynamic analysis
Elucidation of the chemical nature of adsorbed species for Pt(111) in H2SO4 solutions by thermodynamic analysis
The nature of the adsorbed species for Pt(111) in sulfuric acid solutions has been elucidated by a careful thermodynamic analysis of the effect of pH on charge density data. This analysis takes advantage of the fact that, for solutions of constant total sulfate + bisulfate concentration, an increase of pH would increase the sulfate concentration, at the expense of decreasing the bisulfate concentration. As a result, sulfate adsorption would be shifted toward lower potentials, while bisulfate adsorption would follow the opposite trend. In the present work, coulostatic data for Pt(111) in (0.2 ? x) M Me2SO4 + x M H2SO4 (Me: Li, Na; x: 10?4 ? 0.2) and (0.1 ? x) M KClO4 + x M HClO4 + 10?3 M K2SO4 (x: 10?4 ? 0.1) solutions are carefully analyzed. It is concluded that sulfate rather than bisulfate adsorption takes place at potentials higher than the potential of zero charge. This result agrees with the fact that similar FTIRRAS bands for adsorbed sulfate species are observed for pH 0.8?3.5 in (0.2 ? x) M K2SO4 + x M H2SO4 solutions
0743-7463
12408-12417
Garcia-Araez, Nuria
9358a0f9-309c-495e-b6bf-da985ad81c37
Climent, Victor
c3ecab58-edb5-4055-8fa0-c0aef0fc60a4
Rodriguez, Paramaconi
5a751a4e-490e-42bb-9c22-7b0fc72e9a09
Feliu, Juan M.
f2a5301a-2886-4f27-b614-99a74a0a9a28
Garcia-Araez, Nuria
9358a0f9-309c-495e-b6bf-da985ad81c37
Climent, Victor
c3ecab58-edb5-4055-8fa0-c0aef0fc60a4
Rodriguez, Paramaconi
5a751a4e-490e-42bb-9c22-7b0fc72e9a09
Feliu, Juan M.
f2a5301a-2886-4f27-b614-99a74a0a9a28

Garcia-Araez, Nuria, Climent, Victor, Rodriguez, Paramaconi and Feliu, Juan M. (2010) Elucidation of the chemical nature of adsorbed species for Pt(111) in H2SO4 solutions by thermodynamic analysis. Langmuir, 26 (14), 12408-12417. (doi:10.1021/la101112b).

Record type: Article

Abstract

The nature of the adsorbed species for Pt(111) in sulfuric acid solutions has been elucidated by a careful thermodynamic analysis of the effect of pH on charge density data. This analysis takes advantage of the fact that, for solutions of constant total sulfate + bisulfate concentration, an increase of pH would increase the sulfate concentration, at the expense of decreasing the bisulfate concentration. As a result, sulfate adsorption would be shifted toward lower potentials, while bisulfate adsorption would follow the opposite trend. In the present work, coulostatic data for Pt(111) in (0.2 ? x) M Me2SO4 + x M H2SO4 (Me: Li, Na; x: 10?4 ? 0.2) and (0.1 ? x) M KClO4 + x M HClO4 + 10?3 M K2SO4 (x: 10?4 ? 0.1) solutions are carefully analyzed. It is concluded that sulfate rather than bisulfate adsorption takes place at potentials higher than the potential of zero charge. This result agrees with the fact that similar FTIRRAS bands for adsorbed sulfate species are observed for pH 0.8?3.5 in (0.2 ? x) M K2SO4 + x M H2SO4 solutions

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Published date: 4 June 2010
Organisations: Electrochemistry

Identifiers

Local EPrints ID: 345752
URI: https://eprints.soton.ac.uk/id/eprint/345752
ISSN: 0743-7463
PURE UUID: d89ac294-6718-4fba-b9e8-1490bea5197d
ORCID for Nuria Garcia-Araez: ORCID iD orcid.org/0000-0001-9095-2379

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Date deposited: 29 Nov 2012 15:02
Last modified: 19 Nov 2019 01:37

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