Ozone (O₃) and oxides of nitrogen (NO[subscript x]) are ubiquitous pollutants in many urban areas around the world. Though they mostly originate outdoors, human inhalation exposure to these pollutants largely occurs indoors, because of the large fraction of our time spent inside buildings. Exposure to O₃ and nitrogen dioxide (NO₂) has been associated with decreased respiratory function, onset of asthma, and cardiovascular events. Through laboratory testing, field exposure and modeling, this study evaluates the feasibility and long-term efficiency of using passive removal materials (PRMs) both indoors and outdoors for removal of O₃ and NO[subscript x]. Three photocatalytic coatings used outdoors and four indoor building materials were tested for their capacity to remove NO[subscript x] and O₃. Since materials outdoors experience a wider range of environmental conditions than indoors, their effects on NO[subscript x] removal by photocatalytic coatings were evaluated through full factorial experiments representative of summertime outdoor conditions in Southeast Texas. Photocatalytic coatings were also exposed to real outdoor environments for a year to assess their long-term viability. Indoor materials were exposed to real indoor environments for a six-month period and tested monthly for their capacity to remove O₃. Carbonyl emissions from these materials before and after exposure to O₃ were also tested at regular intervals during the six-month period. Finally, removal capacity of NO and NO₂ by new indoor building materials was tested as well. For outdoor PRMs, results suggest that the effect of certain environmental parameters (contact time, relative humidity, temperature) on NO[subscript x] removal effectiveness are consistent across different photocatalytic coatings, while other effects are coating specific. The type of semiconductor used and resistance to wear of the coating are important factors in its ability to retain removal efficacy over time. For indoor PRMs, two of the four materials tested, an activated carbon mat and perlite-based ceiling tiles, exhibited consistent O₃ removal effectiveness over time with low carbonyl emissions, both before and after ozonation. All materials except for activated carbon mat had higher post-ozonation than pre-ozonation emissions. Post-ozonation emissions were dominated by nonanal. Simulation of the use of indoor and outdoor PRMs on a model building through multi-zone/CFD modeling showed that indoor PRMs alone could lead to concentration reductions up to 18 % for O₃ and 23 % for NO₂ in rooms of the model building selected. Addition of PRMs on the outside of the building led to small reductions in pollutant concentrations in the air infiltrating into the building, leading to negligible changes in indoor concentrations. / text

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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Lithium ion batteries have been successful in portable electronics market due to their high energy density, adopting the layered LiCoO₂ as the cathode material in commercial lithium ion cells. However, increasing interest in lithium ion batteries for electric vehicle and hybrid electric vehicle applications requires alternative cathode materials due to the high cost, toxicity, and limited power capability of the layered LiCoO₂ cathode. In this regard, spinel LiMn₂O₄ has become appealing as manganese is inexpensive and environmentally benign, but LiMn₂O₄ is plagued by severe capacity fade at elevated temperatures. This dissertation explores the factors that control and limit the electrochemical performance of spinel LiMn₂O₄ cathodes and focuses on improving the performance parameters such as the capacity, cyclability, and rate capability of various spinel cathodes derived from LiMn₂O₄. From a systematic investigation of a number of cationic and anionic (fluorine) substituted spinel oxide compositions, the improvements in electrochemical properties and performances are found to be due to the reduced manganese dissolution and suppressed lattice parameter difference between the two cubic phases formed during the charge-discharge process. Investigations focused on fluorine substitution reveal that spinel LiMn[subscript 2-yz]LiyZnzO[subscript 4-eta]F[subscript eta] oxyfluoride cathodes synthesized by solid-state reactions at 800 °C employing ZnF₂ as a raw material and spinel LiMn[subscript 2-y-z]Li[subscript y]Ni[subscript z]O[subscript 4-eta]F[subscript eta] oxyfluoride cathodes synthesized by firing the cation-substituted LiMn[subscript 2-y-z]LiyNi[subscript z]O₄ oxides with NH₄HF₂ at a moderate temperature of 450 °C show superior cyclability, increased capacity, reduced Mn dissolution, and excellent storage performance compared to the corresponding oxide analogs and the conventional LiMn₂O₄. Spinel-layered composite cathodes are found to exhibit better electrochemical performance with graphite anode when charged to 4.7 V in the first cycle followed by cycling at 4.3-3.5 V compared to the normal cycling at 4.3 - 3.5 V. The improved performance is explained to be due to the trapping of trace amounts of protons that may be present in the electrolyte within the layered oxide lattice during the first charge to 4.7 V and the consequent reduction in Mn dissolution. Electrochemical performances of 3 V spinel Li₄Mn₅O₁₂ cathodes are also improved by fluorine substitution due to the suppression of the disproportionation of Li4Mn5O12 during synthesis and the formation of the Li₂MnO₃ phase.

Oxide interfaces have attracted considerable attention in recent years due to emerging novel properties that do not exist in the corresponding parent compounds. Furthermore, modern atomic-scale growth and probe techniques enable the formation and study of new artificial interface states distinct from the bulk state. A central issue in controlling the novel behavior in oxide heterostructures is to understand how various physical variables (spin, charge, lattice and/or orbital hybridization) interact with each other. In particular, density function theory (DFT) has provided significant insight into underlying physics of materials at the atomic level, giving quantitative results consistent with experiment. In this dissertation using density functional theory methods, we explore the electronic, magnetic and structural properties developed near the interface in SrTiO3/LaAlO3, EuO/LaAlO3, Fe/PbTiO3/Pt, Fe//BaTiO3/Pt and Cs/SrTiO3 heterostructures. We study the interplay between physical interactions, and quantify parameters that determine physical properties of hetetrostructures. These theoretical studies help understanding how physical variables couple with each other and how they determine new properties at oxide interfaces. / text

We have studied a continuous aerosol process for producing oxide nanoparticles with sizes of 10-60 nm that are decorated with smaller 1-3 nm metallic nanoparticles. Such particles may be useful in a number of areas including catalysis and as contrast enhancement agents in biomarkers. To produce the oxide nanoparticle carriers, an aerosol of 1-10 [micrometer] oxide particles are ablated using an excimer laser. The resulting oxide nanoparticle aerosol is then mixed with 1-2 [micrometer] metallic particles and this mixed aerosol is ablated a second time. The oxide nanoparticles are too small to ablate but act as seeds for the nucleation of metallic nanoparticles on the surface of the oxide. The nanoparticle sizes can be varied by changing the gas type or gas pressure in the aerosol. We demonstrate the feasibility of such an approach using two oxides, SiO₂ and TiO₂, and two metals, Au and Ag. / text

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