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A surface disordering was observed in situ when well-defined anatase TiO2 rhombohedral nanoparticles were exposed to 1 Torr H2O vapor and 10suns light inside the environmental TEM. The disordering is believed to be related to high density of hydroxyl groups formed on surface oxygen vacancies during water splitting reactions.
Pt co-catalyst on TiO2 is able to split pure water producing H2 and O2. The H2 production rate drops during the reaction. Particle size growth during reaction was discovered with Z-contrast images. The particle size growth is believed to be a photo-electro-chemical Ostwald ripening.
Characterizations were also carried out on a more complicated photocatalyst system: Ni/NiO core/shell co-catalyst on TiO2. A decrease of the H2 production rate resulting from photo-corrosion was observed. The Ni is believed to be oxidized to Ni2+ by OH• radicals which are intermediate products of H2O oxidation. The mechanism that the OH• radicals leak into the cores through cracks on NiO shells is more supported by experiments.
Overall this research has done a comprehensive ex situ and in situ TEM characterizations following some typical TiO2 based photocatalysts during reactions. This research has shown the technique availability to study photocatalyst inside TEM in photocatalytic conditions. It also demonstrates the importance to follow structure changes of materials during reactions in understanding deactivation mechanisms.
Three dilemmas plague governance of scientific research and technological
innovation: the dilemma of orientation, the dilemma of legitimacy, and the dilemma of control. The dilemma of orientation risks innovation heedless of long-term implications. The dilemma of legitimacy grapples with delegation of authority in democracies, often at the expense of broader public interest. The dilemma of control poses that the undesirable implications of new technologies are hard to grasp, yet once grasped, all too difficult to remedy. That humanity has innovated itself into the sustainability crisis is a prime manifestation of these dilemmas.
Responsible innovation (RI), with foci on anticipation, inclusion, reflection, coordination, and adaptation, aims to mitigate dilemmas of orientation, legitimacy, and control. The aspiration of RI is to bend the processes of technology development toward more just, sustainable, and societally desirable outcomes. Despite the potential for fruitful interaction across RI’s constitutive domains—sustainability science and social studies of science and technology—most sustainability scientists under-theorize the sociopolitical dimensions of technological systems and most science and technology scholars hesitate to take a normative, solutions-oriented stance. Efforts to advance RI, although notable, entail one-off projects that do not lend themselves to comparative analysis for learning.
In this dissertation, I offer an intervention research framework to aid systematic study of intentional programs of change to advance responsible innovation. Two empirical studies demonstrate the framework in application. An evaluation of Science Outside the Lab presents a program to help early-career scientists and engineers understand the complexities of science policy. An evaluation of a Community Engagement Workshop presents a program to help engineers better look beyond technology, listen to and learn from people, and empower communities. Each program is efficacious in helping scientists and engineers more thoughtfully engage with mediators of science and technology governance dilemmas: Science Outside the Lab in revealing the dilemmas of orientation and legitimacy; Community Engagement Workshop in offering reflexive and inclusive approaches to control. As part of a larger intervention research portfolio, these and other projects hold promise for aiding governance of science and technology through responsible innovation.
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
This dissertation examines the use of Gram-positive thermophilic (60 ◦C) ARB in MXCs since very little is known regarding the behavior of these microorganisms in this setting. Here, we begin with the draft sequence of the Thermincola ferriacetica genome and reveal the presence of 35 multiheme c-type cytochromes. In addition, we employ electrochemical techniques including cyclic voltammetry (CV) and chronoamperometry (CA) to gain insight into the presence of multiple pathways for extracellular electron transport (EET) and current production (j) limitations in T. ferriacetica biofilms.
Next, Thermoanaerobacter pseudethanolicus, a fermentative ARB, is investigated for its ability to ferment pentose and hexose sugars prior to using its fermentation products, including acetate and lactate, for current production in an MXC. Using CA, current production is tracked over time with the generation and consumption of fermentation products. Using CV, the midpoint potential (EKA) of the T. pseudethanolicus EET pathway is revealed.
Lastly, a cellulolytic microbial consortium was employed for the purpose ofassessing the feasibility of using thermophilic MXCs for the conversion of solid waste into current production. Here, a highly enriched consortium of bacteria, predominately from the Firmicutes phylum, is capable of generating current from solid cellulosic materials.
In recent years, a more sustainable approach integrating economic, socio-cultural and environmental impacts has been suggested when analyzing short term event such as festivals. It is important for event managers and scholars alike to understand these potential impacts as heritage festivals continue to evolve and prevalent part of heritage tourism.
This study aims to measure and quantify the economic, social and environmental impacts of two heritage festivals – Gold Rush Days and Bluegrass Festival, closely following Andersson and Lundberg’s 2013 study on commensurability and sustainability utilizing willingness to pay (WTP) and willingness to accept (WTA). Both are annual heritage festivals and take place in Wickenburg, Arizona. Primary data collection methods are used to gather information regarding economic and social impacts. Paper questionnaires distributed via stratified random sample to festival attendees and town residents is the survey instrument used in the study. To determine environmental impacts, secondary data in the form of stakeholder interviews are conducted.
Findings suggest a positive economic impact to the town of Wickenburg. Visitor expenditures, retained local spending and direct, indirect, and induced impacts are presented. Social impacts show a generally positive attitude toward the festival from a resident perspective. Environmental impacts show that collaboration among town stakeholders is needed to better determine festival environmental impact as no formal measures of impact are currently being recorded. Further empirical research is needed to better determine these impacts.
By taking advantage of the prior information obtained from WAXS, a rather crude nano-crystalline model was initialized for further numerical reconstruction. Using Markov-Chain stochastic method, a hundreds of nanometer size $\beta$-sheet distribution model was reconstructed from experimental SAXS data, including silk fiber sampled from \textit{Latrodectus hesperus}, \textit{Nephila clavipes}, \textit{Argiope aurantia} and \textit{Araneus gemmoides}. The reconstruction method was implemented using MATLAB and C++ programming language and can be extended to study a broad range of disordered material systems.