In order to understand better the defect structure and dynamics associated with lower valent dopants complexed with native defects in group IV oxides, In/Cd perturbed angular correlation spectroscopy was performed in ceria and zirconia. Examining the orientation symmetry axis of defects in ceria single crystals at low temperature has allowed the identification of a cadmium with a bound near-neighbor oxygen-vacancy complex as well as a complex involving a cadmium with two opposing, near-neighbor oxygen vacancies. The orientation of the symmetry axis of a third complex is reported; however, this information is not sufficient to identify it. Complementing these low temperature studies, the dynamics of the cadmium/oxygen-vacancy interaction in zirconia at high temperatures was studied. The motion of the oxygen vacancy at high temperatures results in a damping of the PAC signal. This damping is not well characterized by the heuristic Marshall-Meares PAC fitting function, and a model is proposed to fit the data in terms of three physical parameters associated with the vacancy's motion. These parameters are the rate at which a bound oxygen vacancy hops among equivalent sites about the probe, the rate at which a bound vacancy detraps, and the rate at which a vacancy is trapped by cadmium. Fits of individual spectra using this model give respective activation energies of 0.3-0.6 eV, 0.9-1.6 eV, and 0.4-0.6 eV. The uncertainty in these energies can most likely be reduced by fitting spectra from multiple temperatures simultaneously. Despite the large uncertainty in the fitted energies, the values are physically reasonable and indicate that the model adequately describes the motion of the oxygen vacancy about cadmium. / Graduation date: 1997

Graduation date: 1994

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Thesis (Ph.D.)--Marshall University, 2009. / Title from document title page. Includes abstract. Document formatted into pages: contains 117 p. Includes bibliographical references p. 114.

Photoelectrochemical cells (PEC) and microbial fuel cells (MFC) are two promising environmental technologies with the purposes of energy production and pollutant degradation. In this study, p-type Cu2O thin film electrodes were synthesized by electrodeposition on the ITO glass. The influences of various electrodeposition conditions, including the deposition potential, temperature, electrolyte pH, substrates and deposition duration on the morphology and the photoelectrochemical properties of the Cu2O films were investigated. The so-called p-type micro-crystal Cu2O thin film photocathodes were synthesized at -0.4 V, 70 °C and pH 10. An innovative composite Cu2O/TiO2 photoelectrode was developed by dip-coating TiO2 on the surface of the Cu2O film. The outer TiO2 layer would help reduce the electron-hole recombination and hence improve the catalyst stability. The photocatalyst was shown to be capable of photocatalytic degradation of model pollutants. Under simulated solar irradiation, methylene blue, acridine orange, and bromocresso brilliant blue G were effectively degraded in the Cu2O-based PEC. The composite Cu2O/TiO2 photoelectrode could further enhance the photodegradation of the dyes. For the study on MFC with the saline wastewater-inoculated MFCs, an electricity output of 581 mW/m2 could be achieved at a NaCl concentration of 200 mM. Based on the characterization of the bioande using the electrochemical impedance spectroscopy (EIS) technique, the R(QR)(QR) model, instead of the conventional R(QR) model, was found to fit well with the EIS data of the carbon cloth bioanode. The results support the two-interface-based physical model for the description of the bioanode, including an interface on the flat electrode and the other for the porous biofilm matrix. The new model was employed to monitor the biofilm formation and development on the carbon clothe anode during the MFC start-up. In addition, photocatalytic MFC was developed by using the Cu2O film as the photocathode for the MFC. With the simulated solar light illumination, the PMFC open circuit voltage could be increased by 200 mV comparing to the MFC test. Moreover, the cathode material (Cu2O) is much less expensive than Pt used by common MFCs. / published_or_final_version / Civil Engineering / Master / Master of Philosophy

published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Field and laboratory studies were performed to estimate fluxes of the a-ace gases nitrogen monoxide (NO), nitrous oxide (N2O), and methane (CH4) in an organic soil, to determine the microbial processes involved, and to assess how soil water and nitrogen controlled flux rates. Metabolic inhibitors showed microbial nitrification to be the major NO source, regardless of the soil moisture content. Nitrification also produced N 2O, but denitrification losses of this gas from flooded, anaerobic soil were much higher. Up to 26% of nitrified N was converted to NO, but most of this (95%) was consumed microbially before it could escape across the soil surface. The NO-consuming process appeared to be co-oxidation by soil heterotrophs, not coupled to energy production. Organic matter content and CO2 production were therefore good predictors of NO oxidation rates across soil types, and NO oxidation was stimulated by manure addition. / Soil water and nitrogen had nonlinear effects on trace gas fluxes, acting on both production and consumption. Kinetic analysis showed that nitrate was a weak noncompetitive inhibitor, but ammonium a strong competitive inhibitor of soil CH4 oxidation at field fertilization rates. However, spatial and temporal factors complicated fertilization effects on CH4 oxidation in situ. Ammonium was immobilized in surface soil and rapidly nitrified, limiting its inhibitory effect on CH 4 oxidation. Fertilizer N stimulated nitrification and denitrification and therefore gaseous N-oxide production, but other, unexpected fertilizer effects were also observed. Ammonium fertilizer decreased NO oxidation rates. Nitrate and other salts stimulated NO and N2O losses during nitrification, an effect apparently related to soil nitrite accumulation. / The controls exerted on trace gas fluxes by soil water were mediated primarily through diffusion rates. Oxygen diffusion controlled the balance of anaerobic (methanogenesis and denitrification) versus aerobic (CH 4 oxidation and nitrification) processes. Soil moisture content also controlled the diffusion rate of atmospheric CH4 to soil methanotrophs, and the escape of gaseous N-oxides from production sites across the soil surface.

No description available.

Thesis (Ph. D.)--Northeastern University, 2008. / Title from title page (viewed May 19, 2009) Graduate School of Engineering, Dept. of Chemical Engineering. Includes bibliographical references p. 271-281).

Thesis (Ph. D.)--West Virginia University, 1999. / Title from document title page. Document formatted into pages; contains x, 265 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references.