Hydrogen production by water-splitting using solar energy and nanostructure photocatalysts is very promising as a renewable, efficient, environmentally clean technology. The key is to reduce the cost of hydrogen production as well as increase the solar-to-hydrogen conversion efficiency by searching for cost-effective photocatalytic materials. In this dissertation, energy efficiency calculation was carried out based on hydrogen production observation to evaluate the nanomaterials activity. The results are important to gain better understanding of water-splitting reaction mechanism. Design, synthesis, characterization/properties and application of these nanomaterials was the road-map to achieve the research objectives. The design of TiO2 is selected based on unique photocatalytic and photovoltaic properties and high stability in aqueous solution. Various structures of nanocomposites TiO2 were designed according to their characteristics and potential activity. TiO2 with quantum dots, nanocomposites thin film, nanofibers, nanorods, nanowires (core/shell), nanotubes, nanopowders, nanoparticles, and nanosphere decorated with low cost metals, sensitized with dye, and doped with nitrogen are designed. Green physical and chemical synthesis methods such as sol-gel techniques, autoclave, microwave, electrospinning, wet impregnation, hydrothermal, chemical vapor deposition, template-based fabrication (porous anodic aluminium oxide membrane), drop casting, dip coating, wet coating were used to synthesize and fabricate the nanomaterials and quantum dots.Both bottom-up and top-down synthesis techniques were used. The ability to control and manipulate the size, shape/geometry, crystal structure, chemical compositions, interaction and interface properties of these materials at nano-scale during the synthesis enable to enhance their thermal, optical, chemical, electrical, …etc properties. Several characterization techniques such as XRD, XPS, EDS, SEM, UV-visible spectra, and optical microscopic and digital camera were also obtained to characterize the properties and confirm to achieve the desired design. The application or processing to test the activity of these nanomaterials for hydrogen production by water-splitting was conducted through extensive experimental program. It was carried out in a one photo-single column experimental set-up to detect hydrogen evolution. A high throughput screening process to evaluate single photo reduction catalysts was established here for simplicity, safety, cost-effective and flexibility of testing nanomaterials for water photoreduction reactivity and hydrogen generation. Therefore, methanol as electron donor or oxidation agent was mixed with water in equal volume ratio in order to prevent the oxygen evolution and only measured the time course of hydrogen production. The primary objectives of this study is to investigate the following (1) The structure-properties relationship through testing quantum dots, nanocomposites thin film, nanofibers, nanorods, nanowires (core/shell), nanotubes, nanopowders, nanoparticles, nanospheres of TiO2 decorated with metals, dye sensitization, and nitrogen-doping. (2) The role of adding electron donors/relays to solution and their effect on semiconductor surface-electrolyte interface under constant conditions such as KI, Mv 2, NaCl, NaHCO3, sea and pure water. (3) Band gap and defect engineering by cation and anion doping. (4) Quantum dots and dye sensitization effect. The nanomaterials activity evaluated based on observed hydrogen production rate (μmol/h/g) experimentally and based on the energy efficiency (percent) calculation. Major findings in this dissertation are (1) A high throughput screening process to evaluate single photoreduction catalysts for solar-hydrogen production by water-splitting was established. (2) nanofibers structure of TiO2 doped with nitrogen, sensitized with dye (Rose Bengal Sodium) and quantum dots (CuInS2), and decorated with metals (Ag) showed the high solar-to-hydrogen conversion efficiency and high hydrogen production rate (3) Simple, safe, inexpensive, robust, efficient and green physical and chemical synthesis methods were used to prepare the nanomaterials and quantum dots. (4) Gaining insight and better understanding of water-splitting reaction mechanism by (a) Studying the structure-properties relationship of nanomaterials (b) Studying the role of additives on surface-interface chemistry of semiconductor and electrolyte (c) Knowing how to reduce the electron-hole recombination reactions to enhance quantum efficiency (d) Extending the absorption of nanomaterials to harness the visible light of solar spectrum radiation by doping and defect chemistry.

<p>Potential electrolytes for dye-sensitized photoelectrochemical solar cells have been synthesized and their applicability has been investigated. Different experimental techniques were used in order to characterize the synthesized electrolytes, such as elemental analysis, electrospray ionisation/mass spectrometry, cyclic voltammetry, dynamic viscosity measurements, as well as impedance, Raman and NMR spectroscopy. Some crystal structures were characterized by using single crystal X-ray diffraction.</p><p>In order to verify the eligibility of the ionic compounds as electrolytes for photoelectrochemical solar cells, photocurrent density/photovoltage and incident photon-to-current conversion efficiency measurements were performed, using different kinds of light sources as solar simulators. In electron kinetic studies, the electron transport times in the solar cells were investigated by using intensitymodulated photocurrent and photovoltage spectroscopy. The accumulated charge present in the semiconductor was studied in photocurrent transient measurements.</p><p>The ionic liquids were successfully used as solar cell electrolytes, especially those originating from the diethyl and dibutyl-alkylsulphonium iodides. The highest overall conversion efficiency of almost 4 % was achieved by a dye-sensitized, nanocrystalline solar cell using (Bu₂MeS)I:I₂ (100:1) as electrolyte (Air Mass 1.5 spectrum at 100 W m^-2), quite compatible with the standard efficiencies provided by organic solvent-containing cells. Several solar cells with iodine-doped metal-iodidebased electrolytes reached stable efficiencies over 2 %. The (Bu₂MeS)I:I₂-containing cells showed better long-term stabilities than the organic solvent-based cells, and provided the fastest electron transports as well as the highest charge accumulation.</p><p>Several polypyridyl-ruthenium complexes were tested as solar cell sensitizers. No general improvements could be observed according to the addition of amphiphilic co-adsorbents to the dyes or nanopartices of titanium dioxide to the electrolytes. For ionic liquid-containing solar cells, a saturation phenomena in the short-circuit current densities emerged at increased light intensities, probably due to inherent material transport limitation within the systems.</p><p>Some iodoargentates and -cuprates were structurally characterized, consisting of monomeric or polymeric entities with anionic networks or layers. A system of metal iodide crownether complexes were employed and tested as electrolytes in photoelectrochemical solar cells, though with poorer results. Also, the crystal structure of a copper-iodide-(12-crown-4) complex has been characterized</p>

Solar hydrogen has the potential to replace fossil fuels with a sustainable energy carrier that can be produced from sunlight and water via &quotewater splitting&quote. This study investigates the use of hematite (Fe&sub2O&sub3) as a photoelectrode for photoelectrochemical water splitting. Fe&sub2O&sub3 has a narrow indirect band-gap, which allows the utilization of a substantial fraction of the solar spectrum. However, the water splitting efficiencies for Fe&sub2O&sub3 are still low due to poor absorption characteristics, and large losses due to recombination in the bulk and at the surface. The thesis investigates the use of nanostructured composite electrodes, where thin films of Fe&sub2O&sub3 are deposited onto a nanostructured metal oxide substrate, in order to overcome some of the factors that limit the water splitting efficiency of Fe&sub2O&sub3. Doped (Si, Ti) and undoped Fe&sub2O&sub3 thin films were prepared using vacuum deposition techniques, and their photoelectrochemical, electrical, optical and structural properties were characterised. The doped Fe&sub2O&sub3 exhibited much higher photoelectrochemical activity than the undoped material, due to an improvement of the surface transfer coefficient and some grain boundary passivation. Schottky barrier modeling of Fe&sub2O&sub3 thin films showed that either the width of the depletion region or the diffusion length is the dominant parameter with a value around 30 nm, and confirmed that the surface charge transfer coefficient is small. An extensive review of the conduction mechanisms of Fe&sub2O&sub3 is presented. ZnO and SnO&sub2 nanostructures were investigated as substrates for the Fe&sub2O&sub3 thin films. Arrays of well-aligned high aspect ratio ZnO nanowires were optimised via the use of nucleation seeds and by restricting the lateral growth of the nanostructures. The geometry of the nanostructured composite electrodes was designed to maximise absorption and charge transfer processes. Composite nanostructured electrodes showed lower quantum efficiencies than equivalent thin films of Fe&sub2O&sub3, though a relative enhancement ofcollection of long wavelength charge carriers was observed, indicating that the nanostructured composite electrode concept is worthy of further investigation. The rate-limiting step for water splitting with Fe&sub2O&sub3 is not yet well understood and further investigations of the surface and bulk charge transfer properties are required in order to design electrodes to overcome specific shortcomings.

Photoelectrochemical cells have been intensively studied in recent years with regard to using thylakoid and photosynthesis system I/II. BBY membrane is another protein complex that has potential to be utilized to build photoelectrochemical cells. Within the BBY membrane lies the highly active photosynthesis system II complex, which upon light activation, generates electrons transported within the electron transport chain during photosynthesis in green plants. This study presents an approach of immobilizing thylakoid or BBY membrane onto gold nanoparticle modified gold plate or multi-walled carbon nanotube (MWCNT) modified indium tin oxide vi (ITO) coated glass substrate. The results show that BBY membrane has higher activity with a value of 168 ± 12 μmol DCIP/(mg Chl*hr) than the thylakoid, which has an activity of 67 ± 7 μmol DCIP/(mg Chl*hr). Further amperometric tests also show that BBY membrane generates a higher current than the thylakoid. We used gold based materials to build the cell first since gold has high electrical conductivity. However, in order to minimize the construction cost of cells, relatively cheap materials such as ITO coated glass and MWCNT were used instead. The surface morphology of cells was characterized using atomic force microscope (AFM) throughout cell modification. When comparing to the cell with gold material, the cell constructed with ITO and MWCNT generated a higher current density. The highest current density was found as 20.44 ± 1.58 μA/cm2 with a system of ITO/MWCNT/BBY. More, the stability of the system was examined and the result shows a decreasing rate of 0.78 %/hour.

III-nitride nanowires (NWs) have been recognized as efficient photoelectrochemical (PEC) devices due to their large surface-to-volume ratio, tunable bandgap, and chemical stability. Doping engineering can help to enhance the PEC performance further. Therefore, addressing the effects of Si and Mg doping on the III-nitride NW photoelectrodes is of great interest. In this study, doping levels of NWs were tuned by the dopant effusion cell temperature of the molecular beam epitaxy (MBE) growth. The successful doping of the III-nitride NWs was confirmed using photoluminescence (PL), Raman spectroscopy, and open circuit potential (OCP) measurements. The ionized dopant concentrations of Si-doped InGaN/GaN NWs were systematically quantified by electrochemical impedance studies (EIS). Due to the three dimensional surfaces of NWs, modified Mott-Schottky formulas were induced to improve the accuracy of ionized dopant concentrations. The highest dopant concentration of Si-doped InGaN NWs can reach 2.1x1018 cm-3 at Tsi = 1120 oC. Accordingly, the estimated band edge potentials of the tested NWs straddled the redox potential of water splitting. The PEC performance of these devices was investigated by linear scan voltammetry (LSV), chronoamperometry tests, and gas evolution measurements. The results were consistent with the quantified dopant concentrations. The current density of n-InGaN NWs doped at TSi = 1120 oC was nine times higher than the undoped NWs. Additionally, the doped NWs exhibited stoichiometric hydrogen and oxygen evolution. By doping Mg into InGaN and GaN segments separately, the p-InGaN/p-GaN NWs demonstrated improved PEC performance, compared with undoped-InGaN/p-GaN and n-InGaN/n-GaN NWs. The p-InGaN/p-GaN NWs exhibited a highly stable current density at ~-9.4 mA/cm2 for over ten hours with steady gas evolution rates (~107 μmol/cm2/hr for H2) at near a stoichiometric ratio (H2: O2~ 1.8:1). This study demonstrated that optimizing the doping level and appropriate band engineering of III-nitride NWs is crucial for enhancing their PEC water splitting performance.

Hydrogen is a carrier energy gas that can be utilized as a clean energy source instead of oil and natural gas. Splitting the water into hydrogen and oxygen is one of the most favorable methods to generate hydrogen. The catalytic properties of molybdenum disulfide (MoS2) could be valuable in this role, particularly due to its unique structure and ability to be chemically modified, enabling its catalytic activity to be further enhanced or made comparable to that of Pt-based materials. In general, these modification strategies may involve either structural engineering of MoS2 or enhancing the kinetics of charge transfer, including by confining to single metal atoms and clusters or integrating with a conductive substrate. We present the results of synergetic integration of MoS2 films with a Si-heterojunction solar cell for generating H2 via the photochemical water splitting approach. The results of the photochemical measurements demonstrated an efficient photocurrent of 36. 3 mA cm-2 at 0 V vs. RHE and an onset potential of 0.56 V vs. RHE. In addition to 25 hours of continuous photon conversion to H2 generation, this study points out that the integration of the Si-HJ with MoS2 is an effective strategy for enhancing the internal conductivity of MoS2 towards efficient and stable hydrogen production. Moreover, we studied the effect of doping an atomic scale of Pt on the catalytic activity of MoS2. The electrochemical results indicated that the optimum single Pt atoms loading amount demonstrated a distinct enhancement in the hydrogen generating, in which the overpotential was minimized to -0.0505 V to reach a current density of 10 mA cm−2 using only 10 ALD cycles of Pt. The Tafel slopes of the ALD Pt/ML-MoS2 electrodes were in the range of 55–120 mV/decade, which indicates a fast improvement in the HER velocity as a result of the increased potential. Stability is another important parameter for evaluating a catalyst. The same (10 ALD cycles) Pt/ML-MoS2 electrode was able to continuously generate hydrogen molecules at for 150 hours. These superior results demonstrate that the low conductivity of semiconductive MoS2 can be enhanced by anchoring the film with Pt SAs and clusters, leading to sufficient charge transport and a decrease in the overpotential.

One way of harnessing and storing our most abundant and renewable energy source, sunlight, is by utilizing it to split water for the hydrogen generation as a storable form of fuel. Si, the most investigated material for solar-to-hydrogen technology has great potential as the single photoelectrode. While some success has been achieved in Si-Based photoelectrochemical (PEC) systems, they suffer from low efficiency and short longevity. Moreover, in order for hydrogen to be commercially viable, the existing challenges of electrical, optical, and catalysis management must be addressed concurrently. Herein, we work on the simultaneous improvement in light harvesting, charge carrier separation/transfer, and catalysis management of Si-based photocathodes, achieving best-in-class efficiency with stable electrochemical performance. By decoupling the light harvesting side from the electrocatalytic surface we nullify parasitic light absorption. We developed a Si bifacial (SiBF) PEC photocathode to absorb light on both sides of PEC devices, which exhibits a current density of 39.01 mA/cm2. Unlike conventional monofacial PEC cells, our bifacial design demonstrates excellent omnidirectional light harvesting capability. Furthermore, back buried junction photoelectrochemical (BBJ-PEC) cells were fabricated that can realize efficient decoupling of photon. This scheme enables maximum light-harvesting without any metal contact, which prevents the shadow effect during the water splitting reaction. The highest hydrogen evolution current density (41.76 mA/cm2) was demonstrated based on a single BBJ-PEC device. Additionally, wireless water splitting can be achieved when three BBJ-PEC cells were connected in series. The efficient PEC cell design described herein demonstrates promising performance, taking us a step closer to real-world solar-to-hydrogen production.

Solid-state dye-sensitized solar cells (ssDSSCs) and recently developed perovskite solar cells (PSCs) have attracted a great attention in the scientific field of photovoltaics due to their low cost, absence of solvent, simple fabrication and promising power conversion efficiency (PCE). In these types of solar cell, the dye molecule or the perovskite can harvest the light on the basis of electron excitation. Afterwards, the electron and hole are collected at the charge transport materials. Photoelectrochemical polymerization (PEP) is employed in this thesis to synthesize conducting polymer hole transport materials (HTMs) for ssDSSCs. We have for the first time developed aqueous PEP in comparison with the conventional organic PEP with acetonitrile as solvent. This water-based PEP could potentially provide a low-cost, environmental-friendly method for efficient deposition of polymer HTM for ssDSSCs. In addition, new and simple precursors have been tested with PEP method. The effects of dye molecules on the PEP were also systematically studied, and we found that (a) the bulky structure of dye is of key importance for blocking the interfacial charge recombination; and (b) the matching of the energy levels between the dye and the precursor plays a key role in determining the kinetics of the PEP process. In PSCs, the HTM layer is crucial for efficient charge collection and its long term stability. We have studied different series of new molecular HTMs in order to understand fundamentally the influence of alkyl chains, molecular energy levels, and molecular geometry of the HTM on the photovoltaic performance. We have identified several important factors of the HTMs for efficient PSCs, including high uniformity of the HTM capping layer, perovskite-HTM energy level matching, good HTM solubility, and high conductivity. These factors affect interfacial hole injection, hole transport, and charge recombination in PSCs. By systematical optimization, a promising PCE of 19.8% has been achieved by employing a new HTM H11. We believe that this work could provide important guidance for the future development of new and efficient HTMs for PSCs.

Inserido no contexto de fontes de energia renováveis, este trabalho consiste na síntese e caracterização de filmes de bastões de ZnO modificados com quantum dots de CdTe a fim de serem aplicados em células fotoeletroquímicas. Bastões de ZnO são materiais interessantes, porque este tipo de estrutura facilita o transporte de portadores de carga, minimizando a perda destes nos contornos de grão, sua recombinação e aniquilação. A modificação do filme de ZnO com nanocristais de CdTe deve aumentar a eficiência da fotoconversão, facilitando a separação de carga e transferência de elétrons, e isso aumenta a estabilidade dos nanocristais, impedindo a corrosão anódica e a decomposição destes. O filme de ZnO foi eletrodepositado potenciostaticamente sobre a superfície de ITO. As análises de MEV e EDX indicaram que filme de ZnO obtido é homogêneo e consiste de bastões com razão atômica de Zn e O de acordo com a estequiometria 1:1. O resultado de DRX apresentou três planos característicos do ZnO na forma cristalina wurtzita. O plano (002) foi o predominante, indicando a orientação dos bastões no eixo c vertical ao substrato. O filme de ZnO tem espessura de 550 nm, bandgap 3,27 eV, potencial de banda plana de 0,4 V e densidade de portadores de carga de 8,9 x 1019 cm-3. O procedimento sintético dos pontos quânticos de CdTe ocorreu a partir da dissolução de óxido de cádmio em ácido tetradecilfosfônico e octadeceno (ODE) a 300 &deg;C. Subsequentemente, a solução precursora de cádmio foi resfriada a 260 &deg;C e então a solução precursora de telúrio, preparada pela dissolução de telúrio e tributilfosfina em ODE, foi injetada. Os nanocristais obtidos foram dispersos em hexano, precitados com etanol e finalmente os quantum dots foram armazenados em tolueno. A partir das análises de UV-Vis e TEM foi possível estimar o tamanho dos pontos quânticos de CdTe com aproximadamente 4 nm. O DRX dos nanocristais de CdTe apresentou os planos característicos principais da estrutura da blenda de zinco. O eletrodo de ZnO modificado com os quantum dots de CdTe (ZnO/CdTe) foi obtido após 24 h de imersão em uma solução de acetonitrila contendo ácido mercaptopropiônico e ácido propiônico. Subsequentemente, o filme de ZnO modificado com o ligante foi imerso por 48 h na dispersão de pontos quânticos de CdTe. O espectro de FTIR revelou a ausência do estiramento simétrico de C=O em 1700 cm-1. Por outro lado o espectro revelou a presença dos modos assimétrico e simétrico vas(CO2-) e vs(CO2-) que foram observados em 1631 e 1417 cm-1, respectivamente. A transformação de Kulbeka-Munk do espectro de reflectância do eletrodo ZnO/CdTe apresentou a banda relativa ao CdTe no mesmo comprimento de onda observado quando este encontrava-se na dispersão. O eletrodo ZnO/CdTe mostrou um valor de fotocorrente de 138 &micro;A, um valor 10 vezes maior que o obtido para o ZnO. Nos experimentos de IPCE (eficiência de conversão do fóton incidente à corrente) um aumento de aproximadamente cinco vezes também foi observado para o eletrodo de ZnO/CdTe. A dinâmica dos portadores de carga foi investigada por TAS (Espectroscopia de Absorção Transiente) nas escalas de tempo fs e &micro;s para os eletrodos de ZnO e de ZnO/CdTe. A análise TAS indicou um tempo de vida menor para o filme ZnO/CdTe em comparação com filme ZnO. A medidas com o eletrodo de Clark demonstraram uma produção de oxigênio pelo eletrodo de ZnO/CdTe. Assim, o filme de ZnO/CdTe proposto apresenta-se como um material promissor para aplicações fotoeletroquímicas. / Placed in the context of renewable energy sources, this work consists of the synthesis and characterization of ZnO films modified CdTe quantum dots to be applied in photoelectrochemical cells. ZnO rods are interesting materials because this kind of structure facilitates the charge carriers transport, minimizing the loss of these at grain boundaries and their recombination and annihilation. The ZnO film modification with CdTe nanocrystals should increase the photoconversion efficiency by facilitating charge separation and electron transfer, and it increases the nanocrystals stability, preventing it from anodic corrosion and decomposition. The ZnO film was electrodeposited potenciostatically on ITO surface. SEM and EDX analysis indicated that the ZnO film obtained is homogeneous and it consists of rods with atomic ratio of Zn and O according to 1:1 stoichiometry. XRD result showed three characteristic planes of ZnO in wurtzite crystalline form. The (002) plane is the predominant, indicating the rods orientation in the c-axis vertical to the substrate. The ZnO film also has a thickness of 550 nm, bandgap of 3.27 eV, flat band potential of 0.4 V and density of charge carriers 8,9 x 1019 cm-3. The synthetic procedure of CdTe quantum dots occurred from the dissolution cadmium oxide in tetradecylphosphonic acid and octadecene (ODE) to 300 &deg;C. Subsequently, cadmium precursor solution of was cooled to 260 &deg;C and then the tellurium precursor solution, prepared by dissolving tellurium in tributylphosphine and in ODE was injected. The obtained nanocrystals were dispersed in hexane, precipitated with ethanol and finally the quantum dots were stored in toluene. From UV-Vis and TEM analysis was possible to estimate the quantum dots size of CdTe as 4 nm. The XRD of CdTe nanocrystals presented the main characteristic planes of zinc blend structure. ZnO electrode modified with CdTe quantum dots (ZnO/CdTe) was obtained by 24 h immersion in a solution of acetonitrile containing mecaptopropionic acid and propionic acid. Subsequently, the ZnO film modified with the linker was immersed for 48 h in CdTe quantum dots dispersion. FTIR spectrum reveals the absence of a symmetrical C=O stretching mode at approximately 1700 cm-1. Instead, the spectrum shows the presence of the asymmetric and symmetric vas(CO2-) and vs(CO2-) modes were observed at 1631 and 1417 cm-1, respectively. Kulbeka-Munk transformation of the reflectance spectrum of the ZnO/CdTe electrode presented the band related to CdTe in the same wavelength observed when this was in the dispersion. The ZnO/CdTe electrode showed a photocurrent value of 138 &micro;A, a value 10 times greater than that obtained for ZnO. At IPCE experiments (incident photon-to-current efficiency) an increase of approximately five times was also noticed to the electrode of ZnO/CdTe. Dynamics of charge carriers was investigated by fs and &micro;s TAS (Transient Absorption Spectroscopy) for ZnO and ZnO/CdTe electrodes. TAS analyses indicate a short life time to ZnO/CdTe electrode compared to ZnO film. Clark electrode measurements showed oxygen production by ZnO/CdTe electrode. Thus, ZnO/CdTe proposed electrode is presented as promising material for photoelectrochemical applications.

Thesis advisor: Dunwei Wang / Solar energy, the most abundant and free renewable energy, holds great promise for humanity's sustainable development. How to efficiently and inexpensively capture, covert solar energy and store it for off peak usages constitutes a grand challenge for the scientific community. Photovoltaic devices are promising candidates but are too costly to be implemented in large scales. On a fundamental level, this is due to the dilemma that the length scales of the optical pathways and electrical pathways often do not match within the photovoltaic device materials. Consider traditional Si solar cell as an example, effective light absorption requires up to hundreds of microns material while the photogenerated charge carries can only diffuse less than a few microns or even shorter before recombination. Such a problem may be solved by using Si nanowires (SiNWs) because vertically aligned nanowires can orthogonalize the light absorption and charge carrier collection pathways, thereby enabling the use of low-cost materials for practically appealing solar energy conversion devices. The objective of this thesis work is to explore low-cost synthesis of vertically aligned SiNW arrays and study their performance in both solar energy conversion and storage devices. We developed a method to synthesize vertically aligned SiNW arrays in a hot-wall chemical vapor deposition system with tunable length, doping level, and diameter for systematical studies. Empowered by the synthetic control, various types of vertical SiNW arrays were characterized by both steady-state (photoelectrochemical measurement) and transient (electrochemical impedance spectroscopy) techniques in a photoelectrochemical cell platform. Additionally, SiNWs were demonstrated to be a promising candidate for photoelectrochemical aromatic ketone reduction and CO₂ fixation. The reactions studied in this thesis are in close resemblance to natural photosynthesis and the resulted product molecules are precursors to nonsteroidal anti-inflammatory drugs, ibuprofen and naproxen. Lastly, vertical transparent conductive oxide nanotubes were prepared from vertical SiNW array templates. Ultrathin hematite (Fe₂O₃) film was coated on the nanotube scaffold by atomic layer deposition to form a heteronanostructure photoelectrode for efficient solar water oxidation. Our results highlight the potential of vertically aligned SiNW arrays in solar cell, solar water splitting and artificial photosynthesis applications. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.