Catalysis is an important part of chemistry. This is also reflected in the chemical industry where 85-90 % of all products are made catalytically. Also nature employs catalysts, i.e. enzymes, for its reactions. To improve on the already existing catalysts one can learn a lot from nature which often uses earth-abundant elements in the enzymes which have also been optimized and finely tuned for billions of years. To gain a deeper understanding of both enzymatic and artificial catalysis one needs to investigate the mechanism of the catalytic process. But for very efficient catalysts with turnover frequencies of several thousand per second this is not easy, since an investigation of the mechanism involves resolving intermediates in the catalytic cycle. The intermediates in these instances are short-lived corresponding to their turnover frequencies. A maximum turnover frequency of 1,000 s-1 e.g. means that each catalyst goes through the whole catalytic cycle in 1 ms. Therefore time-resolved techniques are necessary that have a faster detection speed than the turnover frequency of the catalyst. Flash photolysis is a spectroscopic technique with an instrument response function down to 10 ns.  Coupling this technique with mid-infrared probing yields an excellent detection system for probing different redox and protonation states of carbonyl metal complexes. Since many catalysts as well as natural enzymes involved in water splitting are metal carbonyl complexes this is an ideal technique to monitor the intermediates of these catalysts. Chapter 3 covers the investigation of [FeFe] hydrogenases, enzymes that catalyze the reduction of protons to hydrogen in nature. Chapter 4 investigates the intermediates of biomimetic complexes, resembling the active site of natural [FeFe] hydrogenases. Chapter 5 covers the insights gained from investigating other catalysts which are also involved in water splitting and artificial photosynthesis.

Thesis advisor: Kian L. Tan / Thesis advisor: Dunwei Wang / Silicon nanowires are utilized to harvest the energy from visible light. The introduction of a nickel pre-catalyst, 1, allows for this energy to be stored in chemical bonds, which are subsequently used in the carboxylation of 4-octyne. / Thesis (MS) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Dunwei Wang / Artificial photosynthesis is achieved by placing a semiconductor in water, where photoexcited charges generate a photovoltage at the surface of the semiconductor. However, solar to fuel efficiencies of earth abundant metal oxides and metal nitrides remain limited by their low photovoltages. Many different treatments have been used to improve the photovoltages of semiconductors, such as photocharging, surface regrowths, or the addition of heterogeneous catalysts. However, in these treatments, it remains unclear whether the enhanced photovoltage arises from improved kinetics or energetics. In many of the following studies, the surface kinetics of different semiconductors are measured in order to quantify how surface kinetics are related to the photovoltage of these materials. Different spectroscopic measurements are made along with detailed analysis of the Fermi level and quasi Fermi level in order to corroborate the kinetic data with energetic data. Together, this dissertation explores a multitude of methods and procedures that demonstrate how the photovoltage of semiconductors can be understood and manipulated for photoelectrochemial artificial photosynthesis. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Integrated photoelectrochemical water splitting with sunlight is one possible solution to growing global energy needs. Integration of catalysts, photoabsorbers and a membrane require low barriers to charge dissipation if a free standing device structure is to be achieved. The n-type/PEDOT:PSS junction has be identified as the major resistive component and constitutes a large barrier to charge dissipation. In this thesis, the modification of the interface between n-type Si/PEDOT:PSS was achieved by growing a highly – doped region at the contact between the wire and the membrane to reduce voltage loss at the junction from 300 mV to 130 mV. In addition, modification of the surface using a thiophene moiety is observed to decrease the voltage loss from 300 mV to 30 mV. Formation of an insulating silicon oxide on the methyl functionalized surface of the microwires identified a need for characterization of planar silicon samples representative of the sides of the microwires. Si (110), (211) and (111) crystal faces were functionalized with a methyl group and showed different resistance to oxidation. The Si (111) surface was the most resistant while the Si (211) surface was observed to be the least resistant to ambient oxidation.

Donor-acceptor systems have unique properties that make them ideal candidates for solar energy harvesting through mimicry of natural photosynthesis. This dissertation is focused on unraveling those unique properties in various types of donor-acceptor systems. The systems investigated are categorized as closely linked, push-pull, supramolecular, and multi-unit. As part of the study, photosynthetic analogues based on BF2-chelated dipyrromethene (BODIPY), porphyrin, phthalocyanine, truxene, ferrocene, quinone, phenothiazine (PTZ), perylenediimide (PDI), fullerene (C60), dicyanoquinodimethane (DCNQ), tetracyanobutadiene (TCBD), and triphenylamine (TPA) are investigated. The effects of proximity between donor-acceptor entities, their geometrical orientation relative to each other, push-pull character of substituents, and competitive energy and electron transfer are examined. In all systems, primary events of photosynthesis are observed, that is absorption and energy transfer and/or electron transfer is witnessed. Ultrafast transient absorption spectroscopy is utilized to characterize the photo-induced events, while other methods such as steady-state luminescence, cyclic voltammetry, differential pulse voltammetry, chronoamperometry, and computational calculations are used to aid in the characterization of the donor-acceptor systems, in particular their applicability as solar energy harvesters.

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.

<p>This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II.</p><p>The redox properties of these complexes have been investigated with electro chemical methods and the structure of the complexes has been investigated with different X-ray techniques. Structural aspects and the effect of water on the redox properties have been shown.</p><p>One of the manganese complexes has been covalently linked in a triad donor-photosensitizer-acceptor (D–P–A) system. The kinetics of this triad has been investigated in detail after photo excitation with both optical and EPR spectroscopy. The formed charge separated state (D^––P–A⁺) showed an unusual long lifetime for triad based on ruthenium photosensitizers.</p><p>The thesis also includes a study of manganese-salen epoxidation reactions that we believe can give an insight in the oxygen transfer mechanism in the water oxidising complex in photosystem II.</p>

This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II. The redox properties of these complexes have been investigated with electro chemical methods and the structure of the complexes has been investigated with different X-ray techniques. Structural aspects and the effect of water on the redox properties have been shown. One of the manganese complexes has been covalently linked in a triad donor-photosensitizer-acceptor (D–P–A) system. The kinetics of this triad has been investigated in detail after photo excitation with both optical and EPR spectroscopy. The formed charge separated state (D––P–A+) showed an unusual long lifetime for triad based on ruthenium photosensitizers. The thesis also includes a study of manganese-salen epoxidation reactions that we believe can give an insight in the oxygen transfer mechanism in the water oxidising complex in photosystem II.

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.

The aim of this study is to investigate and reveal challenges in photocatalytic CO2 reduction tests performed in liquid media. Effect of test conditions in photocatalytic studies are often underestimated with an assumption of negligible mass transfer limitations in observed rate results. In this study, effect of mass transfer limitations in liquid phase photocatalytic tests was revealed with stirring rate and gas hold-up time experiments performed with Pt/TiO2 and Cu/TiO2 catalysts. In addition, apparent activation energies of 12 and 19.5 kJ/mol found with Pt/TiO2 and Cu/TiO2 catalysts respectively indicate diffusion limitations which favor back oxidation reactions resulting in low reduction yields. Photocatalytic CO2 reduction reaction is named as Artificial Photosynthesis even though present artificial system does not have sophisticated transport and membrane systems which natural systems have. Similarities and differences between artificial and natural photosynthesis are studied in order to present ideas to improve present photocatalytic rates. Kinetic and microkinetic modeling of catalytic methanol production from CO2 hydrogenation on Cu surfaces were performed in order to have an idea about kinetic limitations at photocatalytic systems. Calculations were performed at temperatures and pressures at which photocatalytic studies are conducted. The results indicated that water has an inhibitory effect on methanol formation rates and higher pressures could be implemented in photocatalytic systems for higher rates. Another implication drawn from degree of rate control calculations is that H formation step plays an important role underlying the importance of water splitting in CO2 reduction reactions.