Richard L. Kurtz

Electrochemical Reduction of CO2 to CH3OH at Copper Oxide Surfaces

The direct reduction of CO2 to CH3OH is known to occur at several types of electrocatalysts including oxidized Cu electrodes. In this work, we examine the yield behavior of an electrodeposited cuprous oxide thin film and explore relationships between surface chemistry and reaction behavior relative to air-oxidized and anodized Cu electrodes. CH3OH yields (43 μmol cm-2 h-1) and Faradaic efficiencies (38%) observed at cuprous oxide electrodes were remarkably higher than air-oxidized or anodized Cu electrodes suggesting Cu(I) species may play a critical role in selectivity to CH3OH. Experimental results also show CH3OH yields are dynamic and the copper oxides are reduced to metallic Cu in a simultaneous process. Yield behavior is discussed in comparison with photoelectrochemical and hydrogenation reactions where the improved stability of Cu(I) species may allow continuous CH3OH generation.

A synchrotron radiation study of BaO films on W(001) and their interaction with H2O, CO2, and O2

The interaction of O2, CO2, and H2O with bulk BaO and BaO adlayers adsorbed on W(001) has been examined using ultraviolet photoelectron spectroscopy. H2O reacts with bulk BaO to form Ba(OH)2, while CO2 forms a surface layer of BaCO3. Water and carbon dioxide also react with a (√2×2)R45–BaO monolayer adsorbed on W(001) to produce adsorbed OH and CO3 species bound to the tungsten substrate. The interaction of O2 with W(001) is enhanced by the presence of a BaO monolayer on the substrate. The observations are compared with the results of previous studies.

High resolution three-dimensional visualization and characterization of coronary atherosclerosis in vitro by synchrotron radiation x-ray microtomography and highly localized x-ray diffraction

Human atherosclerotic plaques in both native and bypass arteries have been visualized using microtomography to provide additional information on the nature of coronary artery disease. Plaques contained within arteries removed from three white males aged 51, 55 and 70 are imaged in three-dimensions with monochromatic synchrotron x-ray radiation. Fields of view are 658 x 658 x 517 voxels. with cubic voxels ranging from 12 to 13 microm on a side. X-ray energies range from 11 to 15 keV (bandpass approximately 10 eV). At lower energies, high local absorption tends to generate reconstruction artefacts, while at higher energies the arterial wall is scarcely visible. At all energies, calcifications are clearly visible and differences are observed between plaques in native arteries (lifetime accumulations) versus bypass arteries (plaques developing in the interval between the heart bypass operation and the autopsy). In order to characterize coronary calcification, a microfocused, 50 microm2, 25 keV x-ray beam was used to acquire powder diffraction data from selected calcifications. Also, large calcifications were removed from the native arteries and imaged with 25 keV x-ray energy. Calcifications are composed of hydroxyapatite crystallites and an amorphous phase. In summary, native calcifications are larger and have a higher fraction of hydroxyapatite than calcifications from the bypass arteries.

Installation and operation of the LNLS double-crystal monochromator at CAMD

A new x‐ray beamline has been installed at CAMD utilizing a two‐crystal monochromator designed and built at LNLS. The beamline will operate in the 2–18 keV range using up to 4 mrad of dipole radiation from the CAMD storage ring. The monochromator maintains a fixed exit beam and fixed positions of the beam on the two crystals using mutually perpendicular elastic translations. With the ring operating at 1.5 GeV and 160 mA, Si(220) crystals will provide a flux of ∼3(109) photons/s/mrad at 8 keV, with an energy resolution ΔE<2 eV, to the experimental hutch. The beamline is equipped with an EXAFS endstation and will also be used for other x‐ray applications at CAMD. First results are presented.

Oxidized ultrathin Fe films on Cu(001)

We report photoemission studies of ultrathin films of the minority-spin conductor, Fe3O4 on a Cu(001) substrate. Fe films are deposited at room temperature and oxidized at 810 K in 10−6 Torr O2. For Fe films less than 2 ML thick, LEED and STM measurements show that oxidation produces mostly an FeO(111) while thicker Fe layers give Fe3O4(111). Photoemission reveals that there is a distinct electronic structure for these two phases. There are also significant differences between the electronic structures of ultrathin oxide films and those of corresponding bulk oxides.

A microtomography beamline at the Louisiana State University Center for Advanced Microstructures and Devices synchrotron

A microtomography beamline has been recently assembled and is currently operating at the Louisiana State University’s Center for Advanced Microstructures and Devices synchrotron (CAMD). It has been installed on a bending magnet white-light beamline at port 7A. With the storage ring operating at 1.5 GeV, this beamline has a maximum usable x-ray energy of ∼15 keV. The instrumentation consists of computer-controlled positioning stages for alignment and rotation, a CsI(Tl) phosphor screen, a reflecting mirror, a microscope objective (1:1, 1:4), and Linux/LabVIEW-controlled charge coupled device. With the 1:4 objective, the maximum spatial resolution is 2.25 μm. The positioning and image acquisition computers communicate via transfer control protocol/internet protocol (TCP/IP). A small G4/Linux cluster has been installed for the purpose of on-site reconstruction. Instrument, alignment and reconstruction programs are written in MATLAB, IDL, and C. The applications to date are many and we present several examples. Several biological samples have been studied as part of an effort on biological visualization and computation. Future improvements to this microtomography station include the addition of a double-multilayer monochromator, allowing one to evaluate the three-dimensional elemental composition of materials. Plans also include eventual installation at the CAMD 7 T wiggler beamline, providing x rays in excess of 50 keV to provide better penetration of higher mass-density materials.

Imaging the Fermi surface of Cu using photoelectron spectroscopy

Abstract We have studied the Fermi surface of Cu using an ellipsoidal-mirror analyzer which gives two-dimensional images of photoelectron intensity versus emission angle. From these images, we have obtained the full Fermi surface of Cu in three-dimensional k -space. Our results are in excellent agreement with previous studies and provide new perspectives on Fermi surface studies.

Electronic Signatures of a Model Pollutant–Particle System: Chemisorbed Phenol on TiO2(110)

Environmentally persistent free radicals (EPFRs) are a class of composite organic/metal oxide pollutants that have recently been discovered to form from a wide variety of substituted benzenes chemisorbed to commonly encountered oxides. Although a qualitative understanding of EPFR formation on particulate metal oxides has been achieved, a detailed understanding of the charge transfer mechanism that must accompany the creation of an unpaired radical electron is lacking. In this study, we perform photoelectron spectroscopy and electron energy loss spectroscopy on a well-defined model system-phenol chemisorbed on TiO2(110) to directly observe changes in the electronic structure of the oxide and chemisorbed phenol as a function of adsorption temperature. We show strong evidence that, upon exposure at high temperature, empty states in the TiO2 are filled and the phenol HOMO is depopulated, as has been proposed in a conceptual model of EPFR formation. This experimental evidence of charge transfer provides a deeper understanding of the EPFR formation mechanism to guide future experimental and computational studies as well as potential environmental remediation strategies.

Imaging the surface state of Cu(111)

We have studied the surface state of Cu(111) using an ellipsoidal‐mirror analyzer which gives two dimensional images of photoelectron intensity versus emission angle. By combining these images, we have obtained the surface‐state dispersion in three dimensional E versus k space. We have also studied the bulk Fermi surface of Cu(100). Our results are in excellent agreement with previous studies and provide a new perspective on studies of surface electronic structure.

Design and synthesis of model and practical palladium catalysts using atomic layer deposition

We investigated the “one-batch” synthesis of model and practical palladium catalysts using atomic layer deposition (ALD). Two types of model catalysts and one type of powder-based nanocatalyst were synthesized simultaneously by ALD under viscous flow conditions. In addition, Pd/TiO2(110) model catalysts were prepared by the identical ALD process but under ultrahigh vacuum conditions. Because of the self-limiting surface reaction that defines ALD, the local structure of all the Pd catalysts were essentially the same as confirmed by a suite of microscopic and spectroscopic characterization techniques. A comprehensive understanding of the Pd-based catalysts was achieved by applying both surface science probes and advanced synchrotron techniques, and by strategically selecting the catalyst substrate best suited for each characterization. Both X-ray absorption spectroscopy and X-ray resonant photoelectron spectroscopy suggested that Pd only weakly interacted with the TiO2 support. The one-batch synthesis approach facilitated by ALD can potentially bridge the “synthesis gap” between model catalysts and practical catalysts.