Matching Items (51)
Description
There has been much interest in photoelectrochemical conversion of solar energy in recent years due to its potential for low-–cost, sustainable and renewable production of fuels. Despite the huge potential, there are still a number of technical barriers due to the many constraints needed in order to drive photoelectrochemical reactions such as overall water splitting and the identification of efficient and effective semiconductor materials. To this end, the search for novel semiconductors that can act as light absorbers is still needed. The copper hydroxyphosphate mineral libethenite (CHP), which has a chemical formula of Cu2(OH)PO4, has been recently shown to be active for photocatalytic degradation of methylene blue under UV-–irradiation, indicating that photo-excited electrons and holes can effectively be generated and separated in this material. However, CHP has not been well studied and many of its fundamental electrochemical and photoelectrochemical properties are still unknown. In this work, the synthesis of different morphologies of CHP using hydrothermal synthesis and precipitation methods were explored. Additionally, a preliminary investigation of the relevant fundamental characteristics such as the bandgap, flatband potential, band diagram, electrochemical and photoelectrochemical properties for CHP was performed. Better understanding of the properties of this material may lead to the development of improved catalysts and photocatalysts from natural sources.
ContributorsLi, Man (Author) / Chan, Candace K. (Thesis advisor) / O'Connell, Michael (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2013
Description
Life cycle assessment (LCA) is a powerful framework for environmental decision making because the broad boundaries called for prevent shifting of burden from one life-cycle phase to another. Numerous experts and policy setting organizations call for the application of LCA to developing nanotechnologies. Early application of LCA to nanotechnology may identify environmentally problematic processes and supply chain components before large investments contribute to technology lock in, and thereby promote integration of environmental concerns into technology development and scale-up (enviro-technical integration). However, application of LCA to nanotechnology is problematic due to limitations in LCA methods (e.g., reliance on data from existing industries at scale, ambiguity regarding proper boundary selection), and because social drivers of technology development and environmental preservation are not identified in LCA. This thesis proposes two methodological advances that augment current capabilities of LCA by incorporating knowledge from technical and social domains. Specifically, this thesis advances the capacity for LCA to yield enviro-technical integration through inclusion of scenario development, thermodynamic modeling, and use-phase performance bounding to overcome the paucity of data describing emerging nanotechnologies. With regard to socio-technical integration, this thesis demonstrates that social values are implicit in LCA, and explores the extent to which these values impact LCA practice and results. There are numerous paths of entry through which social values are contained in LCA, for example functional unit selection, impact category selection, and system boundary definition - decisions which embody particular values and determine LCA results. Explicit identification of how social values are embedded in LCA promotes integration of social and environmental concerns into technology development (socio-enviro-technical integration), and may contribute to the development of socially-responsive and environmentally preferable nanotechnologies. In this way, tailoring LCA to promote socio-enviro-technical integration is a tangible and meaningful step towards responsible innovation processes.
ContributorsWender, Ben A. (Author) / Seager, Thomas P (Thesis advisor) / Crozier, Peter (Committee member) / Fraser, Matthew (Committee member) / Guston, David (Committee member) / Arizona State University (Publisher)
Created2013
Description
High temperature CO2 perm-selective membranes offer potential for uses in various processes for CO2 separation. Recently, efforts are reported on fabrication of dense ceramic-carbonate dual-phase membranes. The membranes provide selective permeation to CO2 and exhibit high permeation flux at high temperature. Research on transport mechanism demonstrates that gas transport for ceramic-carbonate dual-phase membrane is rate limited by ion transport in ceramic support. Reducing membrane thickness proves effective to improve permeation flux. This dissertation reports strategy to prepare thin ceramic-carbonate dual-phase membranes to increase CO2 permeance. The work also presents characteristics and gas permeation properties of the membranes. Thin ceramic-carbonate dual-phase membrane was constructed with an asymmetric porous support consisting of a thin small-pore ionic conducting ceramic top-layer and a large pore base support. The base support must be carbonate non-wettable to ensure formation of supported dense, thin membrane. Macroporous yttria-stabilized zirconia (YSZ) layer was prepared on large pore Bi1.5Y0.3Sm0.2O3-δ (BYS) base support using suspension coating method. Thin YSZ-carbonate dual-phase membrane (d-YSZ/BYS) was prepared via direct infiltrating Li/Na/K carbonate mixtures into top YSZ layers. The thin membrane of 10 μm thick offered a CO2 flux 5-10 times higher than the thick dual-phase membranes. Ce0.8Sm0.2O1.9 (SDC) exhibited highest CO2 flux and long-term stability and was chosen as ceramic support for membrane performance improvement. Porous SDC layers were co-pressed on base supports using SDC and BYS powder mixtures which provided better sintering comparability and carbonate non-wettability. Thin SDC-carbonate dual-phase membrane (d-SDC/SDC60BYS40) of 150 μm thick was synthesized on SDC60BYS40. CO2 permeation flux for d-SDC/SDC60BYS40 exhibited increasing dependence on temperature and partial pressure gradient. The flux was higher than other SDC-based dual-phase membranes. Reducing membrane thickness proves effective to increase CO2 permeation flux for the dual-phase membrane.
ContributorsLu, Bo (Author) / Lin, Yuesheng (Thesis advisor) / Crozier, Peter (Committee member) / Herrmann, Macus (Committee member) / Forzani, Erica (Committee member) / Lind, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2014
Description
Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates.
ContributorsRaghavan, Rahul (Author) / Chan, Candace K. (Thesis advisor) / Crozier, Peter (Committee member) / Petuskey, William T (Committee member) / Arizona State University (Publisher)
Created2013
Description
Geopolymers, a class of X-ray amorphous, ceramic-like aluminosilicate materials are produced at ambient temperatures through a process called geopolymerization. Due to both low energy requirement during synthesis and interesting mechanical and chemical properties, geopolymers are grabbing enormous attention. Although geopolymers have a broad range of applications including thermal/acoustic insulation and waste immobilization, they are always prepared in monolithic form. The primary aim of this study is to produce new nanostructured materials from the geopolymerization process, including porous monoliths and powders.
In view of the current interest in porous geopolymers for non-traditional applications, it is becoming increasingly important to develop synthetic techniques to introduce interconnected pores into the geopolymers. This study presents a simple synthetic route to produce hierarchically porous geopolymers via a reactive emulsion templating process utilizing triglyceride oil. In this new method, highly alkaline geopolymer resin is mixed with canola oil to form a homogeneous viscous emulsion which, when cured at 60 °C, gives a hard monolithic material. During the process, the oil in the alkaline emulsion undergoes a saponification reaction to decompose into water-soluble soap and glycerol molecules which are extracted to yield porous geopolymers. Nitrogen sorption studies indicates the presence of mesopores, whereas the SEM studies reveals that the mesoporous geopolymer matrix is dotted with spherical macropores. The method exhibits flexibility in that the pore structure of the final porous geopolymers products can be adjusted by varying the precursor composition.
In a second method, the geopolymerization process is modified to produce highly dispersible geopolymer particles, by activating metakaolin with sodium silicate solutions containing excess alkali, and curing for short duration under moist conditions. The produced geopolymer particles exhibit morphology similar to carbon blacks and structured silicas, while also being stable over a wide pH range.
Finally, highly crystalline hierarchical faujasite zeolites are prepared by yet another modification of the geopolymerization process. In this technique, the second method is combined with a saponification reaction of triglyceride oil. The resulting hierarchical zeolites exhibit superior CO2-sorption properties compared to equivalent commercially available and currently reported materials. Additionally, the simplicity of all three of these techniques means they are readily scalable.
In view of the current interest in porous geopolymers for non-traditional applications, it is becoming increasingly important to develop synthetic techniques to introduce interconnected pores into the geopolymers. This study presents a simple synthetic route to produce hierarchically porous geopolymers via a reactive emulsion templating process utilizing triglyceride oil. In this new method, highly alkaline geopolymer resin is mixed with canola oil to form a homogeneous viscous emulsion which, when cured at 60 °C, gives a hard monolithic material. During the process, the oil in the alkaline emulsion undergoes a saponification reaction to decompose into water-soluble soap and glycerol molecules which are extracted to yield porous geopolymers. Nitrogen sorption studies indicates the presence of mesopores, whereas the SEM studies reveals that the mesoporous geopolymer matrix is dotted with spherical macropores. The method exhibits flexibility in that the pore structure of the final porous geopolymers products can be adjusted by varying the precursor composition.
In a second method, the geopolymerization process is modified to produce highly dispersible geopolymer particles, by activating metakaolin with sodium silicate solutions containing excess alkali, and curing for short duration under moist conditions. The produced geopolymer particles exhibit morphology similar to carbon blacks and structured silicas, while also being stable over a wide pH range.
Finally, highly crystalline hierarchical faujasite zeolites are prepared by yet another modification of the geopolymerization process. In this technique, the second method is combined with a saponification reaction of triglyceride oil. The resulting hierarchical zeolites exhibit superior CO2-sorption properties compared to equivalent commercially available and currently reported materials. Additionally, the simplicity of all three of these techniques means they are readily scalable.
ContributorsMedpelli, Dinesh (Author) / Seo, Dong-Kyun (Thesis advisor) / Herckes, Pierre (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2015
Description
Transparent conductive oxides (TCO) comprise a class of materials that exhibit unique combination of high transparency in the visible region along with high electrical conductivity. TCOs play an important role as transparent electrodes for optoelectronic devices such as solar cell panels, liquid crystal displays, transparent heat mirrors and organic light emitting devices (OLED). The most commonly used transparent electrodes in optoelectronic applications is indium tin oxide (ITO) due to its low resistivity (~ 10−4 Ω-cm) and high transmittance (~ 80 %). However, the limited supply of indium and the growing demand for ITO make the resulting fabrication costs prohibitive for future industry. Thus, cost factors have promoted the search for inexpensive materials with good electric-optical properties.
The object of this work is to study the structure-property-processing relationship and optimize a suitable transparent electrode with the intent to optimize them for flexible optoelectronics applications. The work focuses on improved processing of the mixed oxide (indium gallium zinc oxide, IGZO) thin films for superior optical and electrical properties. The study focuses on two different methods of post-deposition annealing-microwave and conventional. The microwave annealing was seen to have the dual advantage of reduced time and lower temperature, as compared to conventional annealing. Another work focuses on an indium free transparent composite electrode (TCE) where a very thin metal layer is inserted between the two TCO layers. A novel Nb2O5/Ag/Nb2O5 multilayered structure can exhibit better electrical and optical properties than a single layered TCO thin film. The focus for low cost alternative leads to a TiO2/metal/TiO2 based TCE. A systematic study was done to understand the effect of metal thickness and substituting different metals (Ag, Cu or Au) on the opto-electrical properties of the TCEs. The TiO2/Ag/TiO2 with mid Ag thickness 9.5 nm has been optimized to have a sheet resistance of 5.7 Ohm/sq. average optical transmittance of 90 % at 550 nm and figure of merit with 61.4 ×10-3 Ω-1. The TCEs showed improved optical and electrical properties when annealed in forming gas and vacuum. These dielectric/metal/dielectric multilayer TCEs have lower total thickness and are more efficient than a single-layer ITO film.
The object of this work is to study the structure-property-processing relationship and optimize a suitable transparent electrode with the intent to optimize them for flexible optoelectronics applications. The work focuses on improved processing of the mixed oxide (indium gallium zinc oxide, IGZO) thin films for superior optical and electrical properties. The study focuses on two different methods of post-deposition annealing-microwave and conventional. The microwave annealing was seen to have the dual advantage of reduced time and lower temperature, as compared to conventional annealing. Another work focuses on an indium free transparent composite electrode (TCE) where a very thin metal layer is inserted between the two TCO layers. A novel Nb2O5/Ag/Nb2O5 multilayered structure can exhibit better electrical and optical properties than a single layered TCO thin film. The focus for low cost alternative leads to a TiO2/metal/TiO2 based TCE. A systematic study was done to understand the effect of metal thickness and substituting different metals (Ag, Cu or Au) on the opto-electrical properties of the TCEs. The TiO2/Ag/TiO2 with mid Ag thickness 9.5 nm has been optimized to have a sheet resistance of 5.7 Ohm/sq. average optical transmittance of 90 % at 550 nm and figure of merit with 61.4 ×10-3 Ω-1. The TCEs showed improved optical and electrical properties when annealed in forming gas and vacuum. These dielectric/metal/dielectric multilayer TCEs have lower total thickness and are more efficient than a single-layer ITO film.
ContributorsDhar, Aritra (Author) / Alford, Terry L. (Thesis advisor) / Petuskey, William (Thesis advisor) / Krause, Stephen (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2015
Description
Gold-silver alloy nanoparticles (NPs) capped with adenosine 5'-triphosphate were synthesized by borohydride reduction of dilute aqueous metal precursors. High-resolution transmission electron microscopy showed the as-synthesized particles to be spherical with average diameters ~4 nm. Optical properties were measured by UV-Visible spectroscopy (UV-Vis), and the formation of alloy NPs was verified across all gold:silver ratios by a linear shift in the plasmon band maxima against alloy composition. The molar absorptivities of the NPs decreased non-linearly with increasing gold content from 2.0 x 108 M-1 cm-1 (fÉmax = 404 nm) for pure silver to 4.1 x 107 M-1 cm-1 (fÉmax = 511 nm) for pure gold. The NPs were immobilized onto transparent indium-tin oxide composite electrodes using layer-by-layer (LbL) deposition with poly(diallyldimethylammonium) acting as a cationic binder. The UV-Vis absorbance of the LbL film was used to calculate the surface coverage of alloy NPs on the electrode. Typical preparations had average NP surface coverages of 2.8 x 10-13 mol NPs/cm2 (~5% of cubic closest packing) with saturated films reaching ~20% of ccp for single-layer preparations (1.0 ~ 10-12 mol NPs/cm2). X-ray photoelectron spectroscopy confirmed the presence of alloy NPs in the LbL film and showed silver enrichment of the NP surfaces by ~9%. Irreversible oxidative dissolution (dealloying) of the less noble silver atoms from the NPs on LbL electrodes was performed by cyclic voltammetry (CV) in sulfuric acid. Alloy NPs with higher gold content required larger overpotentials for silver dealloying. Dealloying of the more-noble gold atoms from the alloy NPs was also achieved by CV in sodium chloride. The silver was oxidized first to cohesive silver chloride, and then gold dealloyed to soluble HAuCl4- at higher potentials. Silver oxidation was inhibited during the first oxidative scan, but subsequent cycles showed typical, reversible silver-to-silver chloride voltammetry. The potentials for both silver oxidation and gold dealloying also shifted to more oxidizing potentials with increasing gold content, and both processes converged for alloy NPs with >60% gold content. Charge-mediated electrochemistry of silver NPs immobilized in LbL films, using Fc(meOH) as the charge carrier, showed that 67% of the NPs were electrochemically inactive.
ContributorsStarr, Christopher A (Author) / Buttry, Daniel A (Thesis advisor) / Petuskey, William (Committee member) / Jones, Anne (Committee member) / Arizona State University (Publisher)
Created2014
Description
There is an inexorable link between structure and stress, both of which require study in order to truly understand the physics of thin films. To further our knowledge of thin films, the relationship between structure and stress development was examined in three separate systems in vacuum. The first was continued copper thin film growth in ultra-high vacuum after adsorption of a sub-monolayer quantity of oxygen. Results showed an increase in compressive stress generation, and theory was proposed to explain the additional compressive stress within the films. The second system explored was the adsorption of carbon monoxide on the platinum {111} surface in vacuum. The experiments displayed a correlation between known structural developments in the adsorbed carbon monoxide adlayer and the surface stress state of the system. The third system consisted of the growth and annealing stresses of ice thin films at cryogenic temperatures in vacuum. It was shown that the growth stresses are clearly linked to known morphology development from literature, with crystalline ice developing compressive and amorphous ice developing tensile stresses respectively, and that amorphous ice films develop additional tensile stresses upon annealing.
ContributorsKennedy, Jordan (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
Fuel cells, particularly solid oxide fuel cells (SOFC), are important for the future of greener and more efficient energy sources. Although SOFCs have been in existence for over fifty years, they have not been deployed extensively because they need to be operated at a high temperature (∼1000 °C), are expensive, and have slow response to changes in energy demands. One important need for commercialization of SOFCs is a lowering of their operating temperature, which requires an electrolyte that can operate at lower temperatures. Doped ceria is one such candidate. For this dissertation work I have studied different types of doped ceria to understand the mechanism of oxygen vacancy diffusion through the bulk. Doped ceria is important because they have high ionic conductivities thus making them attractive candidates for the electrolytes of solid oxide fuel cells. In particular, I have studied how the ionic conductivities are improved in these doped materials by studying the oxygen-vacancy formations and migrations. In this dissertation I describe the application of density functional theory (DFT) and Kinetic Lattice Monte Carlo (KLMC) simulations to calculate the vacancy diffusion and ionic conductivities in doped ceria. The dopants used are praseodymium (Pr), gadolinium (Gd), and neodymium (Nd), all belonging to the lanthanide series. The activation energies for vacancy migration between different nearest neighbor (relative to the dopant) positions were calculated using the commercial DFT code VASP (Vienna Ab-initio Simulation Package). These activation energies were then used as inputs to the KLMC code that I co-developed. The KLMC code was run for different temperatures (673 K to 1073 K) and for different dopant concentrations (0 to 40%). These simulations have resulted in the prediction of dopant concentrations for maximum ionic conductivity at a given temperature.
ContributorsAnwar, Shahriar (Author) / Adams, James B (Thesis advisor) / Crozier, Peter (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
In-situ environmental transmission electron microscopy (ETEM) is a powerful tool for following the evolution of supported metal nanoparticles under different reacting gas conditions at elevated temperatures. The ability to observe the events in real time under reacting gas conditions can provide significant information on the fundamental processes taking place in catalytic materials, from which the performance of the catalyst can be understood. The first part of this dissertation presents the application of in-situ ETEM studies in developing structure-activity relationship in supported metal nanoparticles. In-situ ETEM studies on nanostructures in parallel with ex-situ reactor studies of conversions and selectivities were performed for partial oxidation of methane (POM) to syngas (CO+H2) on Ni/SiO2, Ru/SiO2 and NiRu/SiO2 catalysts. During POM, the gas composition varies along the catalyst bed with increasing temperature. It is important to consider these variations in gas composition in order to design experiments for in-situ ETEM. In-situ ETEM experiments were performed under three different reacting gas conditions. First in the presence of H2, this represents the state of the fresh catalyst for the catalytic reaction. Later in the presence of CH4 and O2 in 2:1 ratio, this is the composition of the reacting gases for the POM reaction and this composition acts as an oxidizing environment. Finally in the presence of CH4, this is the reducing gas. Oxidation and reduction behavior of Ni, Ru and NiRu nanoparticles were followed in an in-situ ETEM under reacting gas conditions and the observations were correlated with the performance of the catalyst for POM. The later part of the dissertation presents a technique for determining the gas compositional analysis inside the in-situ ETEM using electron energy-loss spectroscopy. Techniques were developed to identify the gas composition using both inner-shell and low-loss spectroscopy of EELS. Using EELS, an "operando TEM" technique was successfully developed for detecting the gas phase catalysis inside the ETEM. Overall this research demonstrates the importance of in-situ ETEM studies in understanding the structure-activity relationship in supported-metal catalysts for heterogeneous catalysis application.
ContributorsChenna, Santhosh (Author) / Crozier, Peter A. (Thesis advisor) / Carpenter, Ray (Committee member) / Sieradzki, Karl (Committee member) / Petuskey, William (Committee member) / Arizona State University (Publisher)
Created2011