Research concentrated on the absorption, transformation, and storage of light energy is useful for the energy challenges faced by humanity. In particular, photocatalysis using solar energy to generate useful fuels has become a primary research goal in the drive to replace fossil fuels for the future. In this dissertation it is shown that poly-tetra(4-aminophenyl)porphyrin (pTAPP) can be oxidatively polymerized using a variety of methods, including electropolymerization, chemical oxidation, and interfacial polymerization and that pTAPP has photocatalytic ability to reduce O2 to H2O2 for a storable fuel. Organic conductive polymers such as pTAPP are attractive catalysts because of their high surface area and ability to coat electrodes. pTAPP in a mixed oxidation state is shown to have both its minimum charge transfer resistance as well as its minimum impedance to electronic conductivity in the film. The UV-vis-NIR absorption spectra of pTAPP with increased oxidative doping are similar to hyperporphyrin spectra, characteristic of a two-plus charge localized on a single porphyrin unit. This suggests the presence of a bipolaron on the individual porphyrin units, and thus a bipolaron conductivity mechanism has been proposed. pTAPP changes color depending on its oxidation state, and therefore is a promising material for electrochromic devices. A novel Pourbaix diagram was created as a means of illustrating the redox and protonation states of pTAPP as a function of changes in pH, applied potential, electrochromic behavior, and electronic conductivity. Both pTAPP and pCoTAPP were shown to be effective catalysts for the reduction of oxygen to hydrogen peroxide, with pCoTAPP a better catalyst than pTAPP. When pCoTAPP is irradiated, oxygen reduction occurs close to the thermodynamic potential, indicating a promising system for storage of solar energy.

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Light absorption in metal catalyst nanoparticles can excite charge carriers to generate hot electron (and complimentary hot holes) with energy higher than the Fermi level. When hot electrons possess energy high enough, they exhibit a high tendency to inject into antibonding orbitals of adsorbates on the photoexcited metal nanoparticles, weakening the corresponding chemical bonds to promote chemical reactions with accelerated reaction kinetics and improved selectivity. Such hot-carrier chemistry has been reported on plasmonic metal nanoparticles, such as silver and gold, which exhibit strong surface plasmon resonances (SPRs) and strong light absorption. However, these metal nanoparticles are not suitable catalysts because their affinity toward interesting molecules is limited. In contrast, most transition metals, such as platinum-group metals and early transition metals, are industrially essential catalysts, but light absorption power in metal nanoparticles is low due to the absence of SPRs in the visible spectral range. Therefore, it is intriguing to explore the potential of hot-carrier catalytic chemistry on photoexcited non-plasmonic metal nanoparticles. Upon the absorption of the same optical power, metal nanoparticles with a small size usually exhibit a high probability of hot electron production and high efficiency of injecting hot electrons into adsorbates. It is challenging to have strong light absorption power and operation stability of the catalyst metal nanoparticles with small sizes. In this thesis, dielectric light antenna, i.e., spherical silica nanoparticles with strong surface scattering resonances near their surfaces, is introduced to support the metal catalyst nanoparticles, enabling improved light absorption power in the metal nanoparticles and operation stability. This thesis focuses on ultrafine rhodium (Rh) nanoparticles (with sizes ranging from 1.7 nm to 4.2 nm) that are widely used as thermal catalysts in many important industry reactions, especially for oxygen-containing species conversion, an oxyphilic feature of Rh nanoparticles. Firstly, this dissertation conducted a comparative study to investigate the influence of silica geometry, nanospheres, and rodlike nanoparticles on the light absorption of Rh nanoparticles. Both silica substrates enhanced the light absorption of loaded Rh nanoparticles due to elongated light scattering paths (random scattering) and enhanced electromagnetic field intensity (resonant scattering). However, silica nanospheres support both resonant scattering and random light scattering modes, exhibiting a higher Rh absorption than the usage of rodlike silica nanoparticles. The light resonant scattering modes on highly symmetrical silica nanospheres enable producing "hot spots" with a much higher electromagnetic field intensity than incident light intensity. This study then investigated the effect of silica geometries on photocatalytic performance. The CO2 hydrogenation was studied as a model reaction. The Rh/silica nanosphere system exhibited a faster photocatalytic kinetic than the case of rodlike silica nanoparticles. It is possibly due to the enhanced light power density around the silica nanospheres. The results give a promise of expanding Rh nanoparticles from thermo-catalysis to photocatalysis. Secondly, this dissertation moves onto accelerating aerobic oxidation of primary alcohols to aldehydes, which was benefited from activated oxygen molecules by hot electron injection. This study found that photoexcited Rh nanoparticles enabled accelerating the alcohol oxidation kinetics by four times at a light power intensity of 0.4 W cm-2, accompanied by a reduced activation energy of 21 kJ mol-1. The derived Langmuir-Hinshelwood rate equation was used to fit the oxygen partial pressure results. Photo-illumination promotes the cleavage of associatively adsorbed oxygen molecules into adsorbed oxygen atoms, reducing the energy barrier. Besides, the silica-supported Rh nanoparticles exhibited a higher photocatalytic performance because of the good colloidal stability and enhanced light absorption of small-sized Rh particles. This part of the dissertation shows the possibility of hot-electron mediated reaction pathways towards a desirable kinetic of alcohol oxidation. Thirdly, it will be meaningful to use the abstracted protons from cheap alcohol sources to reduce other organic molecules rather than dangerous hydrogen gas. This dissertation then investigated the possibility of using an isopropanol solvent as a hydrogen source to reduce nitrobenzene and the feasibility of enhancing the selectivity of the reaction with the light illumination. The results showed that the isopropanol was spontaneously oxidized, producing acetone. Light illumination onto Rh particles selectively enhanced the coupling of reduced nitrobenzene intermediates to produce azoxybenzene. The selectivity of nitrobenzene and production rates gradually increased with a higher number of light photons. Photo-illumination promotes both aniline and azoxybenzene production rates. Hot electrons on Rh particles possibly enabled activating nitrobenzene molecules and increasing concentrations of reduced nitrobenzene intermediates. It resulted in a higher possibility of condensation product and azoxybenzene selectivity, which could not be obtained by elevating temperature without light illumination. This part of the work demonstrated the feasibility of hot electrons from Rh nanoparticles to tune the reaction selectivity in a liquid phase. Lastly, it is challenging to modulate the selectivity of CH4 from CO2 hydrogenation because of the competitive CO production. This dissertation moves towards enhancing both kinetic rates and selectivity of CH4 for gaseous CO2 hydrogenation by photoexcited Rh nanoparticles. Light illumination onto Rh/silica nanosphere particles resulted in the selectivity of CH4 over 99% in contrast to ~70% under dark conditions at 330 oC and with an absorbed light power intensity of 1.5 W cm-2. The activation energy of CH4 production and CO2 consumption gradually decreased with higher light power intensity because of the transient injection of hot electrons into adsorbates to activate intermediates. Increasing operating temperature and light power intensity synergistically enhanced the reaction kinetics. Besides, a middle-sized Rh nanoparticle showed a better photocatalytic performance than that of the largest-sized Rh nanoparticles because of the balance in hot-electron production efficiency and intrinsic catalytic performance. Partial pressure dependence and in situ infrared characterizations showed that the critical stable intermediates for CH4 production should be hydrogenated CO2 species (HCOO* COOH*) and hydrogenated CO* species (carbonyl hydride or HxCO*). The light illumination exclusively enhanced the dissociation of CO2 and CO* without apparent influence on CO* desorption. Under high reaction temperature, light illumination preferred a faster CO* conversion than CO2 dissociation, leading to high CH4 selectivity. This result was also supported by higher methanation rates of CO gas under light illumination. The infrared result showed a reduced stretching frequency of CO*, which supported the possibility of the electron from Rh back-donating into antibonding orbitals of strongly adsorbed CO* species. However, hot electrons from silver nanoparticles with a weak COOH* or CO* adsorption could not efficiently activate carbon-species and could not promote CO2 hydrogenation kinetics. This dissertation offers an avenue of enhancing light absorption of small-sized Rh nanoparticles and expanding its usage from thermal catalysis to photocatalysis for driving oxidation and reduction reactions. The reactants share a common feature containing oxygen elements, a strong affinity with rhodium metal for efficient hot electron injection. We studied the light power intensity and temperature-dependence, showing the accelerated reaction kinetics by hot electron-driven pathways. Photo-excited rhodium nanoparticles were believed to promote the cleavage of chemical bonds O-O, N-O, and C-O to drive chemical transformations. The findings offer insights into developing the scope of non-plasmonic metal nanoparticles in photocatalytic reactions for industrial applications. / Chemistry

Access to clean water is essential for human health and dignity. The increasingly rapid population growth, combined with the emergence of resistant chemical compounds and more concentrated toxic residues in the effluent streams of treatment plants, point towards a decline in freshwater resources resulting in a global water crisis in the next decades. Current wastewater treatment plants rely on Advanced Oxidation Processes (AOPs) for the tertiary (or advanced) step of the treatment. Photocatalysis is one of such processes, by which semiconductors are exposed to radiation of specific wavelengths (traditionally UV) to generate Reactive Oxygen Species (ROS) that can degrade organic molecules through a chain of radical oxidation reactions. Anatase titania (TiO2) has been used for many decades as a photocatalyst. Its electronic band structure has a band gap of 3.2 eV, requiring radiation in the UV range to trigger its photocatalytic properties. One way to reduce the band gap energy and shift the absorption peak wavelength to the visible part of the spectrum (thus reducing operation costs) is by doping the photocatalyst particles with transition metal atoms. Iron (III) is a great candidate due to the placement of its conduction/valence bands within titania’s band gap, its atomic radius similar to titanium (IV) and its variety of oxidation states. However, iron-doped anatase titania synthesized by ordinary sol-gel methods shows a photodegradation efficiency that is much lower than undoped anatase. Previous studies have shown that this is caused by an inconspicuous iron oxide layer on the surface of the catalyst particle, forming a physical barrier to the mobility of charge carriers that trigger the formation of ROS radicals. Small changes to the synthesis protocol, namely slowing down the hydrolysis of the Ti precursor by lowering the solution’s pH and acid-washing the final product, have been shown to result in particles that are photoactive under visible radiation and boast an unobstructed reactive surface. In this work, the novel Fe-TiO2 photocatalyst is studied and characterized in terms of its particle size distribution, inner structure and composition using electron microscopy techniques. It is important to know the particle size profile arising from this novel synthetic method, as the presence of nanoparticles could pose a health risk whereas an abundance of oversized particles is undesirable from the perspective of chemical reaction engineering (low surface-to-volume ratio). Inner structure/composition analyses could reveal whether the iron content inside the photocatalyst segregates into iron oxides, which would hinder reaction rates by behaving as a recombination center for charge carriers. As well, gathering more information about the inner structure of the catalyst (such as degree of crystallinity) is desirable as that could help fine-tune the synthesis protocol in order to obtain optimal photocatalytic activity. The particle size distribution studies using scanning electron microscopy revealed that the catalyst samples contain a significant fraction of nanoparticles (31.55% smaller than 100 nm), even though those particles represent a very small fraction of total sample volume (0.00015%) and reactive area (0.03%). Moreover, oversized particles (bigger than 5 m) account for the biggest fraction of sample volume and reactive surface. It was suggested that the size distribution of the catalyst be shifted to intermediate particle sizes by introducing additional grinding and separation steps into the synthesis protocol. The inner structure studies were carried using a combination of scanning, transmission and scanning-transmission electron microscopy, as well as spectroscopy methods such as EDX and EELS to map composition. It was found that the original anatase lattice structure remained unchanged in terms of interplanar spacings and crystallographic orientations, indicating that the addition of iron impurities at the small concentrations used here (0.5at%) did not result in discernible changes to the lattice. The monocrystalline units of Fe-TiO2 (termed crystallites) often appear to be bound together by amorphous material. No segregation of Fe was observed inside the particles at this concentration, as shown by the apparent homogenous composition of the catalyst across crystalline and amorphous regions. The external iron oxide contamination layer observed in previous studies was theorized to form during the later steps of the sol-gel process due to the precipitation of the iron content in solution that failed to be incorporated into the TiO2 gel network. More in-depth studies must be carried to assess whether preferential segregation of iron within the catalyst could occur at higher dopant concentrations. / Graduate

With the increasing demand for energy consumption and the limitations of traditional carbon-based energy sources, the importance of renewable energy generation is undeniable. Among the various methods for generating and storing energy, green hydrogen production through photocatalytic water splitting has gained significant interest. However, despite numerous studies dedicated to finding the perfect material, achieving large-scale industrial applications is still a distant goal. Metal-Organic Frameworks (MOFs) have emerged as a particularly intriguing option due to their exceptional tunability and versatility. Nevertheless, there remains a substantial gap in our understanding of their performance and fundamental aspects. In this study, we focus on Ti-based MOFs, which have shown great promise owing to the redox properties of titanium. We introduce a novel Ti-oxo chain pyrene MOF called ACM- 1, which exhibits remarkable activity in both the hydrogen evolution reaction (HER) and organic transformations. This outstanding performance can be attributed to the high mobility of photogenerated electrons and the strong localization of holes within the material. To further enhance the photocatalytic activity of ACM-1, we employ defect engineering techniques, specifically fluorination of the metal-oxo units. The introduction of fluorine effectively reduces the band gap of the material, leading to improved light absorption capabilities and a significant boost in photocatalytic performance. Additionally, we synthesize a new MOF named ICGM-1, which shares isochemical characteristics with the well-studied MIL-125-NH2. Despite the identical NH2-bdc linker, ICGM-1 differs in terms of its Ti-sbu composition, providing a unique opportunity to investigate the influence of node geometry on photocatalytic activity. Our study reveals that the rod-type geometry is unfavorable due to lower electron charge mobility, highlighting the importance of node architecture in designing efficient photocatalysts. Finally, we report the synthesis of two new Zr-based MOFs, ACM-10 and ACM-11, based on the redox-active TTFT linker. Through Ti grafting, we demonstrate the potential of ACM-10 for HER, further expanding the range of viable MOF photocatalysts.

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