Matthew Patterson

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.

Atomic layer deposition of ZnO on Cu-nanoclusters for methanol synthesis

The properties of ALD-grown ZnO thin films on Cu clusters supported on ZnO(101¯0) have been studied with scanning tunneling and scanning electron microscopy in combination with angle-resolved x-ray photoelectron spectroscopy. Deposition at room temperature of two monolayers of Cu on ZnO(101¯0) results in metallic Cu0 clusters ∼8 nm wide by 1.4 nm high. Higher coverages of 15 ML results in a similar morphology, with slightly larger cluster sizes. Following air-exposure and ALD-growth of two cycles of ZnO, the Cu exhibits Cu+ species characteristic of Cu2O and the thin ZnO coating is hydroxylated. Electrochemical studies of ALD ZnO coatings on Cu suggest that they are more active for CO2 reduction.

High-throughput Toroidal Grating Beamline for Photoelectron Spectroscopy at CAMD

A 5 meter toroidal grating (5m-TGM) beamline has been commissioned to deliver 28 mrad of bending magnet radiation to an ultrahigh vacuum endstation chamber to facilitate angle resolved photoelectron spectroscopy. The 5m-TGM beamline is equipped with Au-coated gratings with 300, 600 and 1200 lines/mm providing monochromatized synchrotron radiation in the energy ranges 25-70 eV, 50–120 eV and 100–240 eV, respectively. The beamline delivers excellent flux (~1014-1017 photons/sec/100mA) and a combined energy resolution of 189 meV for the beamline (at 1.0 mm slit opening) and HA-50 hemispherical analyzer was obtained at the Fermi level of polycrystalline gold crystal. Our preliminary photoelectron spectroscopy results of phenol adsorption on TiO2 (110) surface reveals the metal ion (Ti) oxidation.

Formation of environmentally persistent free radicals (EPFRs) on ZnO at room temperature: Implications for the fundamental model of EPFR generation

Environmentally persistent free radicals (EPFRs) have significant environmental and public health impacts. In this study, we demonstrate that EPFRs formed on ZnO nanoparticles provide two significant surprises. First, EPR spectroscopy shows that phenoxy radicals form readily on ZnO nanoparticles at room temperature, yielding EPR signals similar to those previously measured after 250°C exposures. Vibrational spectroscopy supports the conclusion that phenoxy-derived species chemisorb to ZnO nanoparticles under both exposure temperatures. Second, DFT calculations indicate that electrons are transferred from ZnO to the adsorbed organic (oxidizing the Zn), the opposite direction proposed by previous descriptions of EPFR formation on metal oxides.