An investigation of oxide films on platinum in sulphuric acid solution by electrochemical and photoelectrochemical techniques

Rudge, Andy; Peter, Laurence M.; Hards, Graham; Potter, Robert J.

doi:10.1016/0022-0728(93)03001-6

Cited by 10 publications

(5 citation statements)

References 46 publications

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“…The reduction peak centered initially at 0.63 V SHE reflects the reduction of the ␣-oxide film, which is consistent with reported data. 2,4,6 The hydrogen adsorption-desorption peaks have been the subject of numerous previous investigations 15,23 and they are not discussed further here.…”

Section: Resultsmentioning

confidence: 99%

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Growth and Properties of Oxide Films on Platinum

Sun

Franc²,

Macdonald

2006

J. Electrochem. Soc.

102

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Electrocatalysts supporting the oxygen electrode reaction are commonly covered with thin oxide films that may have a profound influence over the kinetics of the reaction. Little is currently known about the role of oxide films on electrocatalysts, particularly with regard to the role of the defect structure. In this work, the physical and defect structures of the oxide film that forms on platinum in 0.5M normalH2SO4 under steady-state conditions have been investigated using electrochemical impedance spectroscopy (EIS) and ARXPS (angle-resolved X-ray photoelectron spectroscopy). Mott-Schottky analysis shows that the film is n-type, indicating that the defects in the film are either platinum interstitials or oxygen vacancies, or both. ARXPS analysis shows that, for potentials between 1.0 and 1.3normalVSHE , a single-layer film develops, with the principal oxidation state for Pt (in the film) being +2 . However, a bi-layer structure was observed for films formed at potentials greater than 1.3normalVSHE and ARXPS analysis shows that these bilayer films comprise an inner layer containing Pt(II) and an outer layer containing Pt(IV) . Optimization of the point defect model on the EIS data yields values for various kinetic parameters that are then used to predict the steady-state thickness and current. Good agreement with experiment is obtained.

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Section: Resultsmentioning

confidence: 99%

“…Several photoelectrochemical studies of anodic oxide films on platinum have been reported. Rudge et al 23 reported that small anodic photocurrents were detected in the potential region where thin oxide films form. The same result was observed by Vinnikov et al 24 and was interpreted as indicating an n-type electronic character.…”

mentioning

confidence: 99%

Growth and Properties of Oxide Films on Platinum

Sun

Franc²,

Macdonald

2006

J. Electrochem. Soc.

102

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“…However, the barrier height is not determined by the distribution functions, but by the Fermi level of the redox species in the solution and the conduction band edge at the film/solution interface. Assuming that the bandgap of the heavily doped platinum oxide film does not change with temperature (bandgaps of 2.4 eV [41] and 3.1 eV [40] have been reported from photo-electrochemical studies), then the change of the barrier height with temperature within the temperature range studied in this work is relatively 1 The Debye length, L Db , of an n-type semiconductor can be estimated as [12]:…”

Section: Theoretical Aspectsmentioning

confidence: 99%

Oxidation of hydrogen on oxidized platinum

Bao

Macdonald

2007

Journal of Electroanalytical Chemistry

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“…V fb = 0.2 V. The photocurrent increased with increasing anodic potential (about 20 μA at 0.8 V). It must be noted that the surface oxide on Pt under an anodic bias also exhibits a photoresponse . The anodic photocurrent of the Pt/PtO x electrode without a CeO 2 layer (Figure S2 in the Supporting Information), however, was sufficiently small as compared to the Pt/CeO 2 electrode (<3 μA at 0.8 V).…”

Section: Resultsmentioning

confidence: 96%

Photoassisted Anodic Electrodeposition of Ceria Thin Films

et al. 2007

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This study investigated the effect of UV light irradiation on a Pt working electrode during the anodic electrodeposition of ceria (CeO 2 ) thin films in an aqueous solution containing Ce 3+ . UV light irradiation on the Pt anode induced the formation of holes in the valence band of anodically preformed CeO 2 nuclei, which serve as photoabsorbers. The resultant holes oxidized Ce 3+ to CeO 2 at the CeO 2 /solution interface as well as at the bare Pt surface. That is, CeO 2 itself acted as a sensitive layer for photoelectrochemical deposition. Although the current efficiency was reduced by the UV irradiation, the deposition amount and crystal size of CeO 2 clearly increased as compared to the dark process. It was verified that the oxygen saturation of the electrolyte solution was also effective in enhancing the deposition. In this paper, the photoelectrochemical deposition mechanism of CeO 2 is discussed in detail, and the positive effects of photoirradiation on film quality are demonstrated.

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An investigation of oxide films on platinum in sulphuric acid solution by electrochemical and photoelectrochemical techniques

Cited by 10 publications

References 46 publications

Growth and Properties of Oxide Films on Platinum

Growth and Properties of Oxide Films on Platinum

Oxidation of hydrogen on oxidized platinum

Photoassisted Anodic Electrodeposition of Ceria Thin Films

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