Matching Items (3)
Description
The sun provides Earth with a virtually limitless source of energy capable of sustaining all of humanity's needs. Photosynthetic organisms have exploited this energy for eons. However, efficiently converting solar radiation into a readily available and easily transportable form is complex. New materials with optimized physical, electrochemical, and photophysical properties are at the forefront of organic solar energy conversion research. In the work presented herein, porphyrin and organometallic dyes with widely-varied properties were studied for solar energy applications. In one project, porphyrins and porphyrin-fullerene dyads with aniline-like features were polymerized via electrochemical methods into semiconductive thin films. These were shown to have high visible light absorption and stable physical and electrochemical properties. However, experimentation using porphyrin polymer films as both the light absorber and semiconductor in a photoelectrochemical cell showed relatively low efficiency of converting absorbed solar energy into electricity. In separate work, tetra-aryl porphyrin derivatives were examined in conjunction with wide-bandgap semiconductive oxides TiO2 and SnO2. Carboxylic acid-, phosphonic acid-, and silatrane-functionalized porphyrins were obtained or synthesized for attachment to the metal oxide species. Electrochemical, photophysical, photoelectrochemical, and surface stability studies of the porphyrins were performed for comparative purposes. The order of surface linkage stability on TiO2 in alkaline conditions, from most stable to least, was determined to be siloxane > phosphonate > carboxylate. Finally, porphyrin dimers fused via their meso and beta positions were synthesized using a chemical oxidative synthesis with a copper(II) oxidant. The molecules exhibit strong absorption in the visible and near-infrared spectral regions as well as interesting electrochemical properties suggesting possible applications in light harvesting and redox catalysis.
ContributorsBrennan, Bradley J (Author) / Gust, Devens (Thesis advisor) / Moore, Thomas A. (Committee member) / Allen, James P. (Committee member) / Arizona State University (Publisher)
Created2012
Description
Nanoporous crystalline oxides with high porosity and large surface areas are promising in catalysis, clean energy technologies and environmental applications all which require efficient chemical reactions at solid-solid, solid-liquid, and/or solid-gas interfaces. Achieving the balance between open porosity and structural stability is an ongoing challenge when synthesizing such porous materials. Increasing porosity while maintaining an open porous network usually comes at the cost of fragility, as seen for example in ultra low density, highly random porous aerogels. It has become increasingly important to develop synthetic techniques that produce materials with these desired properties while utilizing low cost precursors and increasing their structural strength. Based on non-alkoxide sol-gel chemistry, two novel synthetic methods for nanoporous metal oxides have been developed. The first is a high temperature combustion method that utilizes biorenewable oil, affording gamma alumina (Al2O3) with a surface area over 300 cm3/g and porosity over 80% and controllable pore sizes (average pore width 8 to 20 nm). The calcined crystalline products exhibit an aerogel-like textural mesoporosity. To demonstrate the versatility of the new method, it was used to synthesize highly porous amorphous silica (SiO2) which exhibited increased mechanical robustness while achieving a surface area of 960 m2/g and porosity of 85%. The second method utilizes sequential gelation of inorganic and organic precursors forming an interpenetrating inorganic/organic gel network. The method affords yttria-stabilized zirconia with surface area over 90 cm3/g and porosity over 60% and controllable pore sizes (average pore width 6 to 12 nm). X-ray diffraction, gas sorption analysis, Raman spectroscopy, nuclear magnetic resonance spectroscopy and electron microscopy were all used to characterize the structure, morphology, and the chemical structure of the newly afforded materials. Both novel methods produce products that show superior pore properties and robustness compared to equivalent commercially available and currently reported materials.
ContributorsLadd, Danielle (Author) / Seo, Don (Thesis advisor) / Häussermann, Ulrich (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2012
Description
Energy storage technologies are essential to overcome the temporal variability in renewable energy. The primary aim of this thesis is to develop reactor solutions to better analyze the potential of thermochemical energy storage (TCES) using non-stoichiometric metal oxides, for the multi-day energy storage application. A TCES system consists of a reduction reactor and an insulated MOx storage bin. The reduction reactor heats (to ~ 1100 °C) and partially reduces the MOx, thereby adding sensible and chemical energy (i.e., charging it) under reduced pO2 environments (~10 Pa). Inert gas removes the oxygen generated during reduction. The storage bin holds the hot and partially reduced MOx (typically particles) until it is used in an energy recovery device (i.e., discharge). Irrespective of the reactor heat source (here electrical), or the particle-inert gas flows (here countercurrent), the thermal reduction temperature and inert gas (here N2) flow minimize when the process approaches reversibility, i.e., operates near equilibrium. This study specifically focuses on developing a reduction reactor based on the theoretical considerations for approaching reversibility along the reaction path. The proposed Zigzag flow reactor (ZFR) is capable of thermally reducing CAM28 particles at temperatures ~ 1000 °C under an O2 partial pressure ~ 10 Pa. The associated analytical and numerical models analyze the reaction equilibrium under a real (discrete) reaction path and the mass transfer kinetic conditions necessary to approach equilibrium. The discrete equilibrium model minimizes the exergy destroyed in a practical reactor and identifies methods of maximizing the energy storage density () and the exergetic efficiency. The mass transfer model analyzes the O2 N2 concentration boundary layers to recommend sizing considerations to maximize the reactor power density. Two functional ZFR prototypes, the -ZFR and the -ZFR, establish the proof of concept and achieved a reduction extent, Δδ = 0.071 with CAM28 at T~950 °C and pO2 = 10 Pa, 7x higher than a previous attempt in the literature. The -ZFR consistently achieved > 100 Wh/kg during >10 h. runtime and the -ZFR displayed an improved = 130 Wh/kg during >5 h. operation with CAM28. A techno-economic model of a grid-scale ZFR with an associated storage bin analyzes the cost of scaling the ZFR for grid energy storage requirements. The scaled ZFR capital costs contribute < 1% to the levelized cost of thermochemical energy storage, which ranges from 5-20 ¢/kWh depending on the storage temperature and storage duration.
ContributorsGhotkar, Rhushikesh (Author) / Milcarek, Ryan (Thesis advisor) / Ermanoski, Ivan (Committee member) / Phelan, Patrick (Committee member) / Wang, Liping (Committee member) / Wang, Robert (Committee member) / Arizona State University (Publisher)
Created2023