Water electrolysis conjugated with renewable energy sources potentially realizes a sustainable society. Although the current electrolyzers operate at extreme pH to maximize the electrolysis efficiency, near-neutral pH conditions may optimize the overall system operation when conjugated with renewable energy sources. In this context, a study on the electrolysis in the mild conditions is essential. The dissertation investigates the water electrolysis in various conditions, with a particular focus placed on milder conditions, to rationalize and improve its performance. Microkinetic analysis was performed for the cathodic half-reaction in conjugation with mass transport evaluation using various electrode materials. The analysis revealed a significant universal influence of electrolyte properties on the reaction performances at near-neutral pH. Investigation of the associated electrolyte properties (ion size, viscosity and activity/fugacity) rationally optimized the reaction conditions. Together with the separately performed studies on the anodic half-reaction and system configurations, the finding was successfully transferred to electrocatalytic and solar-driven water splitting systems. The presented herein is a fundamental yet crucial aspect of water electrolysis, which can advance the water electrolysis for the future.

Along with many other solar energy conversion processes, research on photocatalytic water splitting to generate hydrogen and oxygen has experienced rapid major development over the past years. Developing an efficient visible-light-responsive photocatalyst has been one of the targets of such research efforts. In this regard, nitride materials, particularly Ta3N5, have been the subject of investigation due to their promising properties. This dissertation focuses on the fundamental parameters involved in the photocatalytic processes targeting overall water splitting using Ta3N5 as a model photocatalyst. The discussion primarily focuses on relevant parameters that are involved in photon absorption, exciton separation, carrier diffusion, carrier transport, and catalytic efficiency. A collection of theoretical and experimental studies of properties associated with Ta3N5 have been utilized to obtain a comprehensive understanding of this material. The fundamental structural and optoelectronic properties of Ta3N5 have been addressed. From the electronic properties, the dielectric constant and effective masses have been calculated. Because of its high dielectric constant and relatively low effective masses, Ta3N5 is promising for photocatalytic reaction applications. Studies of lattice dynamics, optical properties, and band positions have been able to clearly show that the synthesized Ta3N5 is essentially non-stoichiometric and that a truly pure phase of Ta3N5 has never been achieved, even though XRD has shown a pure phase sample. The photophysical properties of Ta3N5, such as the absorption coefficient, carrier mobility, and carrier lifetime, have been experimentally measured by synthesizing Ta3N5 thin films. Very low kinetic properties with very low transport properties and fast carrier recombination explained why overall water splitting has never been achieved with Ta3N5 as a photocatalyst to date. The extent to which the surface states of Ta3N5 photocatalysts affect photocatalytic performance has been investigated. The surface topmost layer is demonstrated to play a critical role in the photocatalytic activity of Ta3N5; further research on the surface properties of Ta3N5 should be conducted to understand and improve charge separation and the resulting photocatalytic activity. Finally, a remarkable improvement in the photocatalytic OER has been achieved with the addition of cobalt as a cocatalyst. There is a trade-off between the optimum contact of hole transfer from bulk Ta3N5 to the surface of the cobalt cocatalyst and providing active sites for the electrochemical reaction. Knowing the characteristics of cobalt on the Ta3N5 surface, further improvement was attempted by adding a noble metal to the CoOx/Ta3N5 photocatalyst system, where a synergetic effect of CoOx and noble metals was observed.

Electrochemical water splitting to hydrogen and oxygen is an attractive approach to store and convert intermittent renewable energy sources. Energy efficient, cost effective and durable electrochemical systems are highly required. Firstly, CeOx coated oxygen evolution electrocatalysts were developed to improve the stability. Unique permselectivity of the CeOx layer was disclosed, which helps to prevent dissolution of active metal site. Because oxygen evolution reaction requires a higher overpotential than hydrogen evolution reaction, kinetically facile oxidation of soluble redox ions was proposed as an alternative anodic reaction, in which the oxidized redox ions can be used for succeeding homogeneous reactions, such as treatment of H2S. How to tune the thermodynamics and the diffusion of candidate redox ions is discussed for a desired application. In addition to the anodic reaction, cathodic hydrogen evolution reaction has to be optimized. To maximize hydrogen evolution performance in near-neutral pH buffered conditions, concentration overpotentials from local pH and hydrogen on a Pt cathode are distinguished by mass transport modelling. Finally, stand-alone module was developed to perform solar-driven redox-mediated H2S splitting to H2 and S under natural solar irradiation.

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 / Water splitting has been recognized as a promising solution to challenges associated with the intermittent nature of solar energy for over four decades. A great deal of research has been done to develop high efficient and cost-effective catalysts for this process. Among which tantalum nitride (Ta₃N₅) has been considered as a promising candidate to serve as a good catalyst for solar water splitting based on its suitable band structure, chemical stability and high theoretical efficiency. However, this semiconductor is suffered from its special self-oxidation problem under photoelectrochemical water splitting conditions. Several key unique properties of graphitic carbon nitride (g-C₃N₄) render it an ideal choice for the protection of Ta₃N₅. In this work, Ta₃N₅/g-C₃N₄ hybrid photoanode was successfully synthesized. After addition of co-catalyst, the solar water splitting performance of this hybrid photoanode was enhanced. And this protection method could also act as a potential general protection strategy for other unstable semiconductors. / Thesis (MS) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Dunwei Wang / Photosynthesis converts solar energy and stores it in chemical forms. It is one of the most important processes in nature. Artificial photosynthesis, similar to nature, can provide us reaction products that can potentially be used as fuel. This process promises a solution to challenges caused by the intermitted nature of solar energy. Theoretical studies show that photosynthesis can be efficient and inexpensive. To achieve this goal, we need materials with suitable properties of light absorption charge separation, chemical stability, and compatibility with catalysts. For large-scale purpose, the materials should also be made of earth abundant elements. However, no material has been found to meet all requirements. As a result, existing photosynthesis is either too inefficient or too costly, creating a critical challenge in solar energy research. In this dissertation, we use inorganic semiconductors as model systems to present our strategies to combat this challenge through novel material designs of material morphologies, synthesis and chemical reaction pathways. Guided by an insight that a collection of disired properties may be obtained by combining multiple material components (such as nanostructured semiconductor, effective catalysts, designed chemical reactions) through heterojunctions, we have produced some advanced systems aimed at solving fundamental challenges common in inorganic semiconductors. Most of the results will be presented within this dissertation of highly specific reaction routes for carbon dioxide photofixation as well as solar water splitting. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Dunwei Wang / Semiconductor devices offer promise for efficient conversion of sunlight into other useful forms of energy, in either photovoltaic or photoelectrochemical cell configurations to produce electrical power or chemical energy, respectively. This dissertation examines ionic and electronic phenomena in some candidate semiconductors and seeks to understand their implications toward solar energy conversion applications. First, copper sulfide (Cu₂S) was examined as a candidate photovoltaic material. It was discovered that its unique property of cation diffusion allows the room-temperature synthesis of vertically-aligned nanowire arrays, a morphology which facilitates study of the diffusion processes. This diffusivity was found to induce hysteresis in the electronic behavior, leading to the phenomena of resistive switching and negative differential resistance. The Cu₂S were then demonstrated as morphological templates for solid-state conversion into different types of heterostructures, including segmented and rod-in-tube morphologies. Near-complete conversion to ZnS, enabled by the out-diffusion of Cu back into the substrate, was also achieved. While the ion diffusion property likely hinders the reliability of Cu₂S in photovoltaic applications, it was shown to enable useful electronic and ionic behaviors. Secondly, iron oxide (Fe₂O₃, hematite) was examined as a photoanode for photoelectrochemical water splitting. Its energetic limitations toward the water electrolysis reactions were addressed using two approaches aimed at achieving greater photovoltages and thereby improved water splitting efficiencies. In the first, a built-in n-p junction produced an internal field to drive charge separation and generate photovoltage. In the second, Fe₂O₃ was deposited onto a smaller band gap material, silicon, to form a device capable of producing enhanced total photovoltage by a dual-absorber Z-scheme mechanism. Both approaches resulted in a cathodic shift of the photocurrent onset potential, signifying enhanced power output and progress toward the unassisted photoelectrolysis of water. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

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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.

The development of efficient catalyst for water oxidation is of paramount importance to artificial photosynthesis, but before this can be achieved a deeper understanding of this reaction is essential. In nature this reaction occurs in a tetranuclear Mn-cluster which serves as the work-horse of oxygenic photosynthesis. This thesis summarises my efforts at developing molecular systems capable of mimicking this complex employing a biomimetic approach. Three different approaches towards this goal are described here-in. The first section describes a screening study, in which a number of manganese complexes were tested to see whether or not they were capable of catalysing the formation of dioxygen when treated with different oxidants (Papers I). For those reactions in which dioxygen formation was observed the reactions were repeated in labelled water and the incorporation of labelled O-atoms was studied by mass spectrometry. This allowed us to determine to what extent water was the source of the evolved dioxygen (Papers II-III). In Chapter three a reported catalyst and a derivative thereof is studied in depth. The influence of changes to the ligand on the oxygen–oxygen bond forming reaction could unfortunately not be reliably addressed, because of the instability of the complexes under “catalytic” conditions. Nevertheless, the study allowed us to revise the “carboxylate shift”-mechanism suggested in the literature (Papers IV-V). Chapter four describes the continuation of my work on ligands featuring the carboxylate ligand motif first introduced in Chapter three. In this study ligands containing multiple binding pockets were designed and synthesised (Paper VI). A better understanding of the mechanism in the natural water oxidising enzyme will facilitate the design of biomimetic complexes, this is discussed in Chapter five. In this work model complexes (Paper VII) are used to study the mechanism by which natures own water oxidising catalyst performs this reaction.