Vladimir Komanicky

Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction

The development of electrocatalytic materials of enhanced activity and efficiency through careful manipulation, at the atomic scale, of the catalyst surface structure has long been a goal of electrochemists. To accomplish this ambitious objective, it would be necessary both to obtain a thorough understanding of the relationship between the atomic-level surface structure and the catalytic properties and to develop techniques to synthesize and stabilize desired active sites. In this contribution, we present a combined experimental and theoretical study in which we demonstrate how this approach can be used to develop novel, platinum-based electrocatalysts for the CO electrooxidation reaction in CO(g)-saturated solution; the catalysts show activities superior to any pure-metal catalysts previously known. We use a broad spectrum of electrochemical surface science techniques to synthesize and rigorously characterize the catalysts, which are composed of adisland-covered platinum surfaces, and we show that highly undercoordinated atoms on the adislands themselves are responsible for the remarkable activity of these materials.

Shape-Dependent Activity of Platinum Array Catalyst

We produced millions of morphologically identical platinum catalyst nanoparticles in the form of ordered arrays epitaxially grown on (111), (100), and (110) strontium titanate substrates using electron beam lithography. The ability to design, produce, and characterize the catalyst nanoparticles allowed us to relate microscopic morphologies with macroscopic catalytic reactivities. We evaluated the activity of three different arrays containing different ratios of (111) and (100) facets for an oxygen-reduction reaction, the most important reaction for fuel cells. Increased catalytic activity of the arrays points to a possible cooperative interplay between facets with different affinities to oxygen. We suggest that the surface area of (100) facets is one of the key factors governing catalyst performance in the electrochemical reduction of oxygen molecules.

Surface X-Ray Speckles: Coherent Surface Diffraction from Au(001)

We present coherent speckled x-ray diffraction patterns obtained from a monolayer of surface atoms. We measured both the specular anti-Bragg reflection and the off-specular hexagonal reconstruction peak for the Au(001) surface reconstruction. We observed fluctuations of the speckle patterns even when the integrated intensity appears static. By autocorrelating the speckle patterns, we were able to identify two qualitatively different surface dynamic behaviors of the hex reconstruction depending on the sample temperature.

Persistent oscillations of x-ray speckles: Pt (001) step flow

We observed well-defined oscillations of speckle intensities from Pt (001) surfaces at high temperatures, persisting for tens of minutes. We used a model of hex-reconstructed terraces to show that the coherent x-rays reflected from the terraces retain their phases relative to the illumination boundary and the observed oscillations come from surface dynamics due to “step-flow” motion. Our results demonstrate a possibility that x-ray speckles can be applied to monitor the real-time evolution of surfaces.

Polarization-dependent resonant anomalous surface X-ray scattering of CO/Pt(111)

Polarization dependence of resonant anomalous surface X-ray scattering (RASXS) was studied for interfaces buried in electrolytes and in high-pressure gas. We find that RASXS exhibits strong polarization dependence when the surface is only slightly modified by adsorption of light elements such as carbon monoxide on platinum surfaces. σ- and π-polarization RASXS data were simulated with the latest version of ab initio multiple scattering calculations (FEFF8.2). Based on the simulation, we find that Pt layer to C distances in the (2 × 2)-3CO structure are ~ 2.0 A and ~ 1.6 A for atop CO and 3-fold CO, respectively. Some considerations are presented for the origin of the polarization dependence in RASXS.

Fabrication and Properties of Gold Single‐Crystal Ultramicroelectrodes

Areas of 80-3500 μm2 are displayed by gold single-crystal ultramicroelectrodes, which were fabricated from gold single crystals grown electrolytically in silicate gels. According to their cyclic voltammograms in 0.01 M HCl, these ultramicroelectrodes behave similarly to electrodes of more normal dimensions with the same crystallographic orientation of the surface.

Ptychographic x-ray imaging of surfaces on crystal truncation rod

Ptychography is a high-resolution imaging technique, which does not require lenses for image magnification and which provides phase contrast with high sensitivity. Here, we propose to use x-ray ptychography for the imaging of surface structure in crystalline samples. We show that ptychography can be used to image atomic step structures using coherent diffraction patterns recorded along the crystal truncation rod of a crystal surface. In a proof-of-concept experiment on a Pt (111) sample, we present ptychographic reconstructions showing features consistent with surface steps. Due to the penetration power of x-rays, this method could find interesting applications for the study of surface structures under buried interfaces or in harsh environments.

Characterization of off-axis MgB2 epitaxial thin films for planar junctions

Using scanning tunneling spectroscopy, we perform a full mapping of the quasiparticle density of states of magnesium diboride (MgB2) epitaxial thin films grown on (110) yttrium stabilized zirconia (YSZ) by hybrid physical-chemical vapor deposition. The films have critical temperatures of 40 K. X-ray measurements show an epitaxial MgB2 growth having the c-axis tilted by 32° with respect to the normal to the substrate, consistent with the atomic force microscopy images of the sample. Scanning tunneling spectroscopy clearly finds that the spectroscopic peak associated to the π gap is reduced on most of the film surface and the feature representative of the σ gap is present, with different intensity, on the majority of the sample’s surface, which is consistent with x-ray measurements.

Layering and Ordering in Electrochemical Double Layers

Electrochemical double layers (EDL) form at electrified interfaces. Whereas the Gouy-Chapman model describes moderately charged EDL, the formation of Stern layers was predicted for highly charged EDL. Our results provide structural evidence for a Stern layer of cations at potentials close to hydrogen evolution in alkali fluoride and chloride electrolytes. Layering was observed by X-ray crystal truncation rods and atomic-scale recoil responses of Pt(111) surface layers. Ordering in the layer was confirmed by glancing-incidence in-plane diffraction measurements.