Martin Ruge, Jakub Drnec, Björn Rahn, Finn Reikowski, David A. Harrington, Francesco Carlà, Roberto Felici, Jochim Stettner, and Olaf M. Magnussen
J. Electrochem. Soc. 2017 164(9): H608-H614
Publication year: 2017

The potential dependent surface structure of Pt(111) electrodes in electrochemical environment was studied by in situ crystal truncation rod measurements and in operando grazing incidence small angle X-ray scattering. Determination of the interface structure in the oxidation region reveal a continuous increase of the coverage of place exchanged atoms toward more positive potentials. The resulting oxide consists of an oxygen rich outer and a Pt-rich inner atomic layer. With increasing potential the oxide approaches a more uniform stoichometry. While place exchange on atomically smooth terraces only occurs above 1.05 V, structural changes of 3D Pt islands, grown by repetitive oxidation/reduction cycles, already commence at 0.8 V, which is assigned to oxidation at Pt steps. Evolution of the 3D island distribution occurs in all stages of the cycles: Whereas Pt oxidation leads to narrowing of the lateral size distribution, vertical island growth occurs during the subsequent reduction.

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