Thesis advisor: Dunwei Wang / Solar water splitting refers to the reaction that converts solar energy into chemical fuel. It is an attractive means to store solar energy. This process, analogous to nature photosynthesis, uses semiconductor to capture and convert solar irradiation and, as such, is called artificial photosynthesis. Despite its promising prospect, the lack of materials that can satisfy all requirements to achieve efficient solar water splitting becomes an important challenge. In this thesis, we aim to develop a strategy of forming heteronanostructure to tackle the challenge faced by metal oxide-based photoanode for water oxidation. The challenge associated with metal oxide-based photoanodes and current approach to alleviate the challenge is first discussed. We propose a strategy of combining multiple components to form heteronanostructure to meet the challenges, in particular the charge transport issue. By introducing a dedicated charge transporter, we fabricate various heteronanostructure including TiO₂/TiSi₂, Fe₂O₃/TiSi₂ and Fe₂O₃/AZO nanotubes to improve the charge collection and therefore overall efficiency. Additionally, the growth of several important metal oxides by atomic layer deposition is developed and its utilization as photoanode for water splitting is studied for the first time. Because this strategy is based on the rational design and synthesis of materials, it has the potential to produce electrodes with a combination of properties that have not been exhibited simultaneously by single-component materials. In addition, the strategy is highly versatile and can incorporate the latest developments produced by parallel efforts. We are confident that the rational design and synthesis of materials such as the strategy proposed here will play an increasingly more important role in energy research. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Dunwei Wang / When their electrodes are made of nanomaterials or materials with nanoscale features, devices for energy conversion and energy storage often exhibit new and improved properties. One of the main challenges in material science, however, is to synthesize these nanomaterials with designed functionality in a predictable way. This thesis presents our successes in synthesizing TiSi₂ nanostructures with various complexities using a chemical vapor deposition (CVD) method. Attention has been given to understanding the chemistry guiding the growth. The governing factor was found to be the surface energy differences between various crystal planes of orthorhombic TiSi₂ (C54 and C49). This understanding has allowed us to control the growth morphologies and to obtain one-dimensional (1D) nanowires, two-dimensional (2D) nanonets and three-dimensional (3D) complexes with rational designs by tuning the chemical reactions between precursors. Among all these morphologies, the 2D nanonet, which is micrometers wide and long but only approximately 15 nm thick, has attracted great interest because it is connected by simple nanostructures with single-crystalline junctions. It offers better mechanical strength and superior charge transport while preserving unique properties associated with the small-dimension nanostructure, which opens up the opportunity to use it for various energy related applications. In this thesis we focus on its applications in lithium ion batteries. With a unique heteronanostructure consisting of 2D TiSi₂ nanonets and active material coating, we demonstrate the performances of both anode and cathode of lithium ion batteries can be highly improved. For anode, Si nanoparticles are deposited as the coating and at a charge/discharge rate of 8400 mA/g, we measure specific capacities >1000 mAh/g with only an average of 0.1% decay per cycle over 100 cycles. For cathode, V₂O₅ is employed as an example. The TiSi₂/V₂O₅ nanostructures exhibit a specific capacityof 350 mAh/g, a power rate up to 14.5 kW/kg, and 78.7% capacity retention after 9800 cycles. In addition, TiSi₂ nanonet itself is found to be a good anode material due to the special layer-structure of C49 crystals. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.