Thesis advisor: Udayan Mohanty / Solar fuel synthesis via photoelectrochemistry represents a promising strategy to achieve solar energy conversion and storage. The improvement of photoelectrochemical water splitting performance lies in choosing suitable photoelectrode materials, followed by strategic optimization of their properties. Among those properties, the interface between the semiconductors and electrolyte is of paramount importance, yet it is still not well understood. In my dissertation, I will mainly focus on understanding and controlling those interfaces, with two study platforms. The first study platform is tantalum nitride (Ta3N5), which is an attractive photoanode material with good optoelectronic properties. However, it suffers from low photovoltage despite of the high theoretical expectation and rapid performance decay when it is used for water oxidation. With the help of various characterization methods, it was found that water or hydroxyl group adsorption on the surface as well as the self-limited surface oxidation during water oxidation led to the positive shift of band edge positions and Fermi level, accompanied with increase of charge transfer resistance on the surface. In consequence, decrease of photovoltage and photocurrent was observed. Two different strategies were developed. The first was to fully isolate Ta3N5 from water with the deposition of uniform protection layer through atomic layer deposition. The second strategy utilized the reaction between Ta¬3N5 and co-catalyst instead of water, which led to the formation of a photo-induced interface that favored the desired chemistry instead of side reactions. The second study platform is a Si buried junction protected by GaN. By tuning the loading amount of Pt nanoparticles on GaN surface, both the photocurrent density and photovoltage of the photocathode was improved. With detailed spectroscopic study, it was implied that both charge transfer kinetics and interfacial energetics could be influenced by the loading of Pt on the surface. / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Orientador: Isaias de Carvalho Macedo / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-11T15:17:55Z (GMT). No. of bitstreams: 1 Seabra_JoaquimEugenioAbel_D.pdf: 2147529 bytes, checksum: e9ebd63f7d029f2346cd2c026285a2cf (MD5) Previous issue date: 2008 / Resumo: O objetivo deste trabalho foi investigar, no cenário prospectivo, as opções tecnológicas que deverão permitir o melhor aproveitamento da biomassa da cana e suas possíveis implicações no contexto das usinas. Além das possibilidades envolvendo o uso mais diversificado da sacarose, este estudo investigou o aproveitamento do bagaço e palha da cana considerando quatro tecnologias: geração de. energia elétrica através da cogeração com ciclos a vapor (opção atualmente comercial); produção de etanol através da hidrólise (opções para curto, médio e longo prazo); geração de energia elétrica a partir da gasificação da biomassa integrada a ciclos combinados (BIG/GT -C C) (opções para médio-longo prazo); e a produção de combustíveis de síntese a partir da gasificação da biomassa (opções para médio-longo prazo). Para cada uma destas opções, foram discutidos os aspectos tecnológicos mais importantes e estimados os rendimentos e custos de sistemas integradps a uma usina de cana, além de terem sido avaliados seus efeitos nos balanços de energia e emissões de GEE. Neste trabalho ficou evidenciado o grande benefício econômico que pode representar o uso diversificado dos açúcares da cana para a produção de produtos de maior valor agregado, como aminoácidos, por exemplo. No caso da fibra da cana, foi avaliado que opções atualmente comerciais já propiciariam a geração de excedentes de energia elétrica superiores a 140 kWh/tc, com custos em tomo de 100 R$/MWh, para os casos de cogeração com alta pressão e uso de alguma palha em conjunto com o bagaço. Para o futuro, sistemas de cogeração com ciclos combinados deverão permitir que os níveis de excedentes ultrapassem os 200 kWh/tc, mas com custos também superiores (> 140 R$/MWh). Pensando na produção de combustíveis, as opções de curto prazo para a conversão bioquímica do bagaço possibilitariam um aumento na produção de etanol de cerca de 20 L/tc (a um custo de ~680 R$/m / Abstract: The objective of the present work was to investigate, in the prospective scenario, the technology options that might lead to a better use of sugar cane biomass and their possible implications in the mills' context. Besides the possibilities involving the diversified use of cane's sugars, this study evaluated the use of bagasse and cane trash considering four technologies: power generation with c~nventional steam cycles (current options); ethanol production through biomass hydrolysis (options for short, middle and long term); power generation through biomass gasification integrated to combined cycles (BIG/GT -CC) (options for middle-Iong term); and the production of synthetic fuels through biomass gasification (options for middle-Iong term). For each one of these options, were discussed the main technological aspects and estimated the yields and costs for systems integrated to cane mills; their effects over energy and GHG emission balances were assessed as well. In this work was evidenced the great economical benefit which would represent the díversífied use of cane's sugars for the production of higher value products, such as amino acids, for example. For the fiber fraction, it was concluded that current commercial options could already lead to electricity surpluses as high as 140 kWh/tc, with costs around 100 R$/MWh, for those configurations with high pressure boilers and using some amount of trash in addition to bagasse. For the future, combined cycles systems might lead to electricity surpluses higher than 200 kWh/tc, but also with higher costs (> 140 R$/MWh). Regarding fuels production, the short term options for biochemical conversion would allow 20 L/tc ethanol production increasing (produced at ~680 R$/m3), while the long term yields could reach 40 L/tc, with costs at 270 R$/m3. For thermochemical conversion, in the middle-Iong term, Fischer- Tropsch liquids, for instance, could be produced with yields closed to 490 MJ/tc, at costs around 30 R$/GJ. As for energy and GHG emission balances, for the current situation the energy ratio of ethanol production was evaluated as 9.4, with a life cycle net avoided emission of 1.8 t C02eq/m3 anhydrous. But for 2020, considering the expectations about the evolution on cane production and the availability of advanced technologies for biomass use, the energy ratio might rise to 14.2, while net avoided emissions would reach 2.9 t C02eq/m3 anhydrous, based on the adoption ofBIG/GT-CC systems for biomass use. Bearing all these aspects in mind, a broader comparison of the effects of these technology options utilization on the overall mill performance is presented in the end of the study, pointing out their implications for the establishment of the future sugar cane bio-refineries / Doutorado / Doutor em Planejamento de Sistemas Energéticos