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.

A novel X-ray diffractometer for studies of liquid-liquid interfaces.

The study of liquid-liquid interfaces with X-ray scattering methods requires special instrumental considerations. A dedicated liquid surface diffractometer employing a tilting double-crystal monochromator in Bragg geometry has been designed. This diffractometer allows reflectivity and grazing-incidence scattering measurements of an immobile mechanically completely decoupled liquid sample, providing high mechanical stability. The available energy range is from 6.4 to 29.4 keV, covering many important absorption edges. The instrument provides access in momentum space out to 2.54 Å(-1) in the surface normal and out to 14.8 Å(-1) in the in-plane direction at 29.4 keV. Owing to its modular design the diffractometer is also suitable for heavy apparatus such as vacuum chambers. The instrument performance is described and examples of X-ray reflectivity studies performed under in situ electrochemical control and on biochemical model systems are given.

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.

Anomalous potential dependence in homoepitaxial Cu(001) electrodeposition: an in situ surface x-ray diffraction study.

Homoepitaxial Cu electrodeposition on Cu(001) in chloride-containing electrolyte was studied by time-resolved in situ surface x-ray diffraction at growth rates up to 38 ML/ min. With increasing Cu electrode potential, transitions from step-flow to layer-by-layer and then to multilayer growth are observed. This potential dependence is opposite to that expected theoretically and found experimentally for the Au(001) homoepitaxial electrodeposition [K. Krug et al., Phys. Rev. Lett. 96, 246101 (2006)]. The anomalous behavior is rationalized by a decisive influence of the ordered c(2 × 2)-Cl adlayer on the surface energy landscape, specifically on the effective change in dipole moment during adatom diffusion.

Operando Identification of the Reversible Skin Layer on Co3O4 as a Three-Dimensional Reaction Zone for Oxygen Evolution.

Co oxides and oxyhydroxides have been studied extensively in the past as promising electrocatalysts for the oxygen evolution reaction (OER) in neutral to alkaline media. Earlier studies showed the formation of an ultrathin CoO x (OH) y skin layer on Co3O4 at potentials above 1.15 V vs reversible hydrogen electrode (RHE), but the precise influence of this skin layer on the OER reactivity is still under debate. We present here a systematic study of epitaxial spinel-type Co3O4 films with defined (111) orientation, prepared on different substrates by electrodeposition or physical vapor deposition. The OER overpotential of these samples may vary up to 120 mV, corresponding to two orders of magnitude differences in current density, which cannot be accounted for by differences in the electrochemically active surface area. We demonstrate by a careful analysis of operando surface X-ray diffraction measurements that these differences are clearly correlated with the average thickness of the skin layer. The OER reactivity increases with the amount of formed skin layer, indicating that the entire three-dimensional skin layer is an OER-active interphase. Furthermore, a scaling relationship between the reaction centers in the skin layer and the OER activity is established. It suggests that two lattice sites are involved in the OER mechanism.

High-speed in situ surface X-ray diffraction studies of the electrochemical dissolution of Au(001).

We present in situ X-ray surface diffraction studies of interface processes with data acquisition rates in the millisecond regime, using the electrochemical dissolution of Au(001) in Cl-containing solution as an example. This progress in time resolution permits monitoring of atomic-scale growth and etching processes at solid-liquid interfaces at technologically relevant rates. Au etching was found to proceed via a layer-by-layer mechanism in the entire active dissolution regime up to rates of ∼20 ML/s. Furthermore, we demonstrate that information on the lateral surface morphology and in-plane lattice strain during the electrochemical process can be obtained.

Transmission Surface Diffraction for Operando Studies of Heterogeneous Interfaces.

Processes at material interfaces to liquids or to high-pressure gases often involve structural changes that are heterogeneous on the micrometer scale. We present a novel in situ X-ray scattering technique that uses high-energy photons and a transmission geometry for atomic-scale studies under these conditions. Transmission surface diffraction gives access to a large fraction of reciprocal space in a single acquisition, allowing direct imaging of the in-plane atomic arrangement at the interface. Experiments with focused X-ray beams enable mapping of these structural properties with micrometer spatial resolution. The potential of this new technique is illustrated by in situ studies of electrochemical surface phase transitions and deposition processes.