Structural Reorganization of Pt(111) Electrodes by Electrochemical Oxidation and Reduction.

The surface restructuring of Pt(111) electrodes upon electrochemical oxidation/reduction in 0.1 M HClO4 was studied by in situ grazing-incidence small-angle X-ray scattering and complementary scanning tunneling microscopy measurements. These methods allow quantitative determination of the formation and structural evolution of nanoscale Pt islands during potential cycles into the oxidation region. A characteristic ripening behavior is observed, where these islands become more prominent and homogeneous in size with increasing number of cycles. Their characteristic lateral dimensions primarily depend on the upper potential limit of the cycle and only slightly increase with cycle number. The structural evolution of the Pt surface morphology strongly resembles that found in studies of Pt(111) homoepitaxial growth and ion erosion in ultrahigh vacuum. It can be fully explained by a microscopic model based on the known surface dynamic behavior under vacuum conditions, indicating that the same dynamics also describe the structural evolution of Pt in the electrochemical environment.

In operando GISAXS studies of mound coarsening in electrochemical homoepitaxy.

Kinetic roughening during electrodeposition was studied by grazing incidence small angle x-ray scattering for the case of Au(001) homoepitaxial growth in Cl- containing electrolytes. The formation and coarsening of an isotropic mound distribution on unreconstructed Au(001) and of [110]-oriented anisotropic mounds on the "hex" reconstructed surface was observed. The lateral mound coarsening is described by a well-defined scaling law. On unreconstructed Au a transition in the coarsening exponent from ≈1/4 to ≈1/3 with increasing potential is found, which can be explained by the pronounced potential dependence of surface transport processes in an electrochemical environment.