Electrochemical Stability of the Reconstructed Fe3 O4 (001) Surface.

Establishing the atomic-scale structure of metal-oxide surfaces during electrochemical reactions is a key step to modeling this important class of electrocatalysts. Here, we demonstrate that the characteristic (√2×√2)R45° surface reconstruction formed on (001)-oriented magnetite single crystals is maintained after immersion in 0.1 M NaOH at 0.20 V vs. Ag/AgCl and we investigate its dependence on the electrode potential. We follow the evolution of the surface using in situ and operando surface X-ray diffraction from the onset of hydrogen evolution, to potentials deep in the oxygen evolution reaction (OER) regime. The reconstruction remains stable for hours between -0.20 and 0.60 V and, surprisingly, is still present at anodic current densities of up to 10 mA cm-2 and strongly affects the OER kinetics. We attribute this to a stabilization of the Fe3 O4 bulk by the reconstructed surface. At more negative potentials, a gradual and largely irreversible lifting of the reconstruction is observed due to the onset of oxide reduction.

In Situ Measurement of the Size Distribution and Concentration of Insulating Particles by Electrochemical Collision on Hemispherical Ultramicroelectrodes.

One of the greatest limitations in electrochemical collision/nanoimpact methods is the inability to quantify the size of colliding species due to the uneven current distribution on a disk ultramicroelectrode UME (so-called edge effect). This phenomenon arises since radial diffusion is greater at the edge than the center of the active electrode surface. One method of solving this problem is fabrication of a hemispherical UME. We describe the fabrication of a hemispherical Hg UME on a disk UME by a solution-based electrochemical method, chronocoulometry. The use of hemispherical Hg UME to detect collisions of individual amine-functionalized polystyrene beads removes the "edge effect" and enables simultaneous measurements of the concentration and the size distribution of colloids in suspension. Using finite element simulations, we deduce a quantitative relation between the distribution of current step size and the size distribution of the bead. The frequency of collision measured for a given size of bead is then converted into a concentration (in mol/L) by a quantification of the relative contributions of migration and diffusion for each size of bead. Under our experimental conditions (low concentration of supporting electrolyte), migration dominates the flux of bead. The average size of polystyrene beads of 0.5 and 1 µm radius obtained by electrochemistry and scanning electron microscopy (SEM) differs by only -8% and -9%, respectively. The total concentration of polystyrene beads of 0.5 and 1 µm radius obtained by electrochemistry is found in close agreement (<10% of error) with their nominal concentrations (25 and 100 fM).

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.

Revealing Dynamic Rotation of Single Graphene Nanoplatelets on Electrified Microinterfaces.

Nanoparticles interact with a variety of interfaces, from cell walls for medicinal applications to conductive interfaces for energy storage and conversion applications. Unfortunately, quantifying dynamic changes of nanoparticles near interfaces is difficult. While optical techniques exist to study nanoparticle dynamics, motions smaller than the diffraction limit are difficult to quantify. Single-entity electrochemistry has high sensitivity, but the technique suffers from ambiguity in the entity's size, morphology, and collision location. Here, we combine optical microscopy, single-entity electrochemistry, and numerical simulations to elucidate the dynamic motion of graphene nanoplatelets at a gold ultramicroelectrode (radius ∼5 µm). The approach of conductive graphene nanoplatelets, suspended in 10 µM NaOH, to an ultramicroelectrode surface was tracked optically during the continuous oxidation of ferrocenemethanol. Optical microscopy confirmed the nanoplatelet size, morphology, and collision location on the ultramicroelectrode. Nanoplatelets collided on the ultramicroelectrode at an angle, θ, enhancing the electroactive area, resulting in a sharp increase in current. After the collision, the nanoplatelets reoriented to lay flat on the electrode surface, which manifested as a return to the baseline current in the amperometric current-time response. Through correlated finite element simulations, we extracted single nanoplatelet angular velocities on the order of 0.5-2°/ms. These results are a necessary step forward in understanding nanoparticle dynamics at the nanoscale.

Epitaxial growth of gold on H-Si(111): the determining role of hydrogen evolution.

The potential dependence of gold electrodeposition on H-terminated Si(111) is studied in acidic electrolyte by means of atomic force microscopy and X-ray diffraction. The Au films (≤66 monolayers (ML)≈16 nm) are found to be (111)-oriented and in strong epitaxy with the Si(111) surface lattice, with two in-plane orientations separated by 180°. The deposit morphology is controlled by the deposition potential and can be islandlike or atomically flat. The flat morphology is accompanied by a preferential growth of 180°-rotated Au planes with respect to the Si bulk lattice which takes place at potentials where the hydrogen evolution reaction occurs. Obtaining ultraflat Au layers on Si(111) contrasts with the commonly observed islandlike morphology of electrodeposited films on semiconductors. This behavior is discussed in terms of a nucleation coupled with hydrogen evolution reaction (HER) and an enhanced Au adatom mobility induced by this reaction.

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.