A aplicação de semicondutores no tratamento de água e efluentes líquidos é uma tecnologia de remediação ambiental promissora, em especial para poluentes orgânicos. Entre os vários semicondutores que também são fotocatalisadores, o TiO2 é amplamente usado em aplicações ambientais, por ser inerte biológica e quimicamente, ter elevado potencial de oxidação, baixo custo e estabilidade frente à corrosão. Entretanto, o TiO2 também tem algumas desvantagens, tais como: ele é excitado apenas por luz UV e requer uma operação unitária adicional (por exemplo, filtração ou centrifugação) para o reuso do catalisador. Para contornar estas limitações, usou-se um procedimento simples para a síntese de um fotocatalisador magnético (Fe3O4/TiO2) com alta área superficial específica e atividade catalítica, quando comparado com o TiO2 P25 da Evonik. O fotocatalisador foi sintetizado através de um procedimento em três etapas: (1) Partículas α-Fe2O3 foram obtidas por precipitação de uma solução de FeCl3.6H2O 0.01 mol L-1, que foi submetida a uma hidrólise forçada à 100°C por 48 h; (2) Partículas de α-Fe2O3/TiO2 foram obtidas por heterocoagulação de oxi-hidróxidos de Ti(IV) sobre as partículas de α-Fe2O3, as quais foram calcinada a 500°C por 2 h; e (3) As partículas \"casaca/caroço\" do fotocatalisador foram obtidas por calcinação a 400°C por 1 h sob atmosfera redutora (H2). A atividade fotocatalítica do material sintetizado foi avaliada aplicando-o no descoramento de uma solução do corante Azul Ácido 9 (C.I. 42090). Os efeitos do pH e da concentração de catalisador foram estimados por meio de um planejamento fatorial 22. Foi obtido um fotocatalisador com área superficial específica de 202 m2 g-1, facilmente separável do meio reacional em aproximadamente 2 min com o auxílio de um ímã. O fotocatalisador apresentou absorção em toda a região do visível. A maior remoção de cor (54%) foi obtida com pH 3,0, 1,0 g L-1 de catalisador e 2 horas de reação. / The use of semiconductors for treating polluted waters and wastewaters is a promising environmental remediation technology, especially for organic pollutants. Among the several semiconductors that are also photocatalysts, TiO2 is extensively used for environmental application, due to its biological and chemical inertness, high oxidation power, low cost, and stability regarding corrosion. However, TiO2 also has some disadvantages, such as: it is only UV-excited and requires an additional unit operation (e.g. filtration or centrifugation) for reuse purposes. In order to work around those limitations, a simple procedure for synthesizing a magnetic photocatalyst (Fe3O4/TiO2), with high specific surface area and good photocatalytic activity when compared to Evonik\'s TiO2 P25, was used. The photocatalyst was synthesized in a three-step procedure: (1) α-Fe2O3 particles were obtained, by precipitation, from FeCl3.6H2O 0.01 mol L-1, which underwent a forced acid hydrolysis at 100°C for 48 h; (2) α-Fe2O3/TiO2 particles were obtained, by heterocoagulation, of Ti(IV) oxide species on the α-Fe2O3, followed by calcination at 500°C for 2 h; and (3) The core/shell photocatalyst particles were obtained by calcination the α-Fe2O3/TiO2 particles at 400°C for 1 h under reducing atmosphere (H2). The photocatalytic activity of the synthesized material was assessed by the color removal of an Acid Blue 9 (C.I. 42090) dye solution. pH and catalyst dosage effects were estimated by a 22 factorial design. Fe3O4/TiO2 core/shell particles with specific surface area of 202 m2 g-1were obtained. They were easily separated from the reaction medium, in approximately 2 min, with the aid of a magnet. The photocatalyst absorbed radiation throughout the visible spectrum. The greatest color removal (54%) was achieved with pH 3.0, 1.0 g L-1 of photocatalyst, and 2 h of reaction.

The thesis deals with photocatalysis of organic pollutants on UV-activated anatase particles, on UV-activated anatase particles with hydrogen peroxide and hydrogen peroxide itself. The measurement is carried out on a pilot plant UV photoreactor. The aim of the thesis is to determine the effectiveness of azo dyes and antibiotics degradation. The level of azo dyes and antibiotics degradation is measured by UV-VIS spectrometry.

This diploma thesis was focused on the preparation of self-cleaning and photocatalyticaly active titanium dioxide thin films. Transparent and porous thin layers of titanium dioxide were prepared from sol-gel containing titanium tetraisopropoxide (TTIP) as precursor with addition polyethylene glycol (PEG). Transparent thin layers of titanium dioxide were also prepared from colloidal solution titanium dioxide. The immobilization of thin titanium dioxide layers was performed by a sol-gel process on the soda lime glasses. Diffusion of sodium cation from soda lime glasses into titanium dioxide layer were blocked. Sol was deposited by printig method – micropiezo deposition. Sol and thin titanium dioxide layers were characterised by the physical-chemical method. For prepared sol viscosity, density and surface tension were measured. Thickness and hydrophilicity of titanium dioxide layers also were studied. The photocatalytic activity of the printed titanium layers were tested via the photocatalytic degradation of the 2,6-dichlorindophenol. The influence of addition PEG into the sol and influence of sol loading was studied. It was found that the addition of PEG into the sol significantly increased the photocatalytic activity of titanium dioxide layers.

Ce travail concerne le développement de nanoparticules de TiO2 et de SiO2 sensibilisées aux photosensibilisateurs pour application dans la photocatalyse et la thérapie photodynamique (PDT). Les NP ont été soit recouverts d'une coquille de polysiloxane, soit modifiés par l'aminopropyltriéthoxysilane (APTES) seul. Les PSs de tétraphényl monocarboxylphosphine (P1-COOH) ou de chlorine e6 (Ce6) ont été couplés aux NP par liaison amide. En photocatalyse, les NP hybrides modifiées par l'APTES, en particulier TiO2-APTES-Ce6, présentent une activité photocatalytique supérieure vis-à-vis de la dégradation du bleu de méthylène et de l’orange de méthyle sur les systèmes cœur-coquille sous lumière solaire et visible. Pour la PDT, des tests in vitro ont été désignés sur la lignée cellulaire de glioblastome U87 à différentes concentrations de NP éclairées à 652 nm. TiO2-APTES-Ce6 a révélé une bonne phototoxicité car la viabilité cellulaire a diminué de 89% après illumination. L'incorporation cellulaire et la localisation de ces NP et de leurs analogues de la silice ont été explorées. Les ROS impliqués dans la photocatalyse et la PDT ont été étudiés / This work addresses the development of dye-sensitized TiO2 and SiO2 nanoparticles (NPs) for application in photocatalysis and photodynamic therapy (PDT). The NPs were either coated with a polysiloxane shell or modified by aminopropyl triethoxysilane (APTES) alone. Monocarboxylic tetraphenyl porphyrin (P1-COOH) or chlorin e6 (Ce6) PSs were coupled to the NPs by amide bond. In photocatalysis, The APTES-modified sensitized NPs, particularly TiO2-APTES-Ce6, exhibit a superior activity towards the degradation of methylene blue and methyl orange over the core-shell systems under solar and visible light. For PDT, in vitro tests were conducted on the glioblastoma cell line U87 at different NPs’ concentrations illuminated at 652 nm. TiO2-APTES-Ce6 revealed a good phototoxicity as the cell viability decreased by 89% after illumination. The cellular uptake and localization of those NPs and their silica analogues were explored. The ROS involved in photocatalysis and PDT were investigated

Degradation of organic contaminants in wastewaters emanating from industrial processing plants could render the water streams reusable for the purpose of reducing water consumption while protecting the environment from harmful pollutants. Organic pollutants can be removed from water using biological processes that mineralise the organics to H2O and CO2. However, mineralisation by biological processes take a long time and in many cases, total mineralisation is impossible to achieve. Alternatively, organics can be completely degraded and mineralised rapidly using chemical and/or photocatalytic advanced oxidation processes (AOP). Both systems have some short comings. In chemical AOP such as Fenton and photo-Fenton reagents, the chemical agents used remain in the water as pollutants requiring further removal. In photocatalytic oxidation processes, most current technologies use UV light as an energy source. The chemical processes are environmentally incompatible, whereas, the “green” photocatalysis is extremely expensive due to the consumption of electricity by high pressure UV light. Forerunner investigators of photocatalysis utilised TiO2 as the photocatalyst of choice. It has major drawbacks of which the most important one is that it is only activated under ultraviolet (UV) light irradiation. This high energy consumption made the process practically unfeasible. Solar energy (natural light and heat from sun) has great prospects with regards to acting as a substitute for UV since it is a renewable and cheaper energy source. This work therefore investigated the development of a heterogeneous all-solid-state Z-scheme silver/ silver chloride/ bismuth oxychloride (Ag/AgCl/BiOCl) photocatalyst that is able to utilise natural light through being activated by visible light irradiation. This will successfully serve as a green alternative in the use of renewable energy for pollution reduction while saving energy. The synthesised photocatalysts were characterised using various techniques. The purity and crystallinity of the synthesised photocatalysts were determined using x-ray diffraction (XRD) while x-ray photoelectron spectroscopy (XPS) was used to determine the elemental composition and chemical states present in the synthesised catalysts as well as confirm the presence of elemental Ag. Fourier-transform infrared spectroscopy (FTIR) specified the functional groups present while the morphology and chemical composition were determined on a scanning electron microscopy (SEM)/ energy dispersive x-ray spectroscopy (EDS). The surface area and pore size were measured on a Brunauer-Emmett-Teller (BET) and thermogravimetric analysis (TGA) was done to determine the thermal degradation of synthesised particles. Ultraviolet-visible spectroscopy (UV-VIS) was done to determine the photoabsorption range and bandgap of the particles as efficiency of photocatalysis is dependent on the properties and morphology of the semiconductor material. Degradation studies were carried out under both visible and UV light irradiation in a batch reactor. The activity of the synthesised Ag/AgCl/BiOCl photocatalyst was compared to that of commonly used TiO2. Specifically, while 60% degradation was achieved under UV light irradiation by both TiO2 and Ag/AgCl/BiOCl photocatalyst, in visible light irradiation, TiO2 measures only 14% in 4 h while Ag/AgCl/BiOCl measures a photodegradation efficiency of 53%. Other factors such as initial organic contaminants concentration, initial catalyst concentration, pH effects and individual compounds effect were also investigated. The reusability of the catalyst was also reported showing stability of the synthesised catalyst as after a total irradiation time of 48 h, 65% phenol degradation was measured. The phenol degradation kinetics were found to fit the widely used first-order Langmuir-Hinshelwood model. The result from the current study proves the feasibility of a novel process for mineralisation of organic compounds in water under cost effective visible light irradiation for the removal of recalcitrant and refractory organics from water. / Dissertation (MEng)--University of Pretoria, 2019. / Chemical Engineering / MEng / Unrestricted

Much of the energy used in the United States and around the globe is obtained from petroleum, natural gas, and coal. Photocatalytic CO2 reduction can be used to transform CO2 to useful fuels and making fossil fuels more renewable. Input of energy is required, and the sun can provide the required energy for this transformation. Photosensitizer, catalyst, and electron donor are required for photocatalytic CO2 reduction. Due to lack of earth-abundant sensitizers, zinc dipyrrin complexes were synthesized by previous group members and have been used as photosensitizers in this research. The ground and excited state electrochemical properties of two zinc dipyrrin complexes were determined in polar and nonpolar solvents and the measured potentials were used to match the zinc sensitizers with an energetically appropriate iron porphyrin catalyst and a benzylthiol sacrificial electron donor. Lastly, pure CO2 gas was used as the source of carbon for the reduction of CO2 by photocatalysis with the zinc photosensitizers, iron catalyst and sacrificial electron donor. The products formed in headspace were analyzed by GC

A specific allotrope of titanium dioxide (anatase) was synthesized with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). its surface chemistry after dehydroxylation was studied by 1H NMR and FT-IR. Influence of surface fluorides on surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR and NMR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O are still present on anatase after dehydroxylation at 350°C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight on the nature of surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed determining the accessibility of the various OH groups spectroscopically observed. A platinum complex, (CH3)2Pt(COD), is then grafted via surface organometallic chemistry (SOMC) on morphology-controlled Anatase TiO2 to generate single, isolated Pt atoms on TiO2 nano-platelets. The resulting material is characterized by FT-IR, High resolution scanning transmission electron microscopy (HRSTEM), NMR, and XAS, and then used to perform photocatalytic water splitting. The photocatalyst with SOMC-grafted Pt shows superior performance in photocatalytic hydrogen evolution and strongly suppresses backwards reaction of H2 and O2 forming H2O under dark conditions, compared to photocatalyst prepared by standard wet impregnation at the same Pt loading. However, single Pt atoms on this surface also rapidly coalesce into nanoparticles under photocatalytic conditions. It was also found that adsorbtion of carbon monoxide gas at room temperature also triggers the aggregation of Pt single atoms into nanoparticles. A detailed mechanism is investigated for the mobility of Pt in the formation of its carbonyls using density functional theory (DFT) calculations.

Photocatalytic solar fuel generation is the most green, sustainable and viable approach to deal with both the ever-growing energy crisis and environmental issues, simultaneously. The work presented in this thesis is focused on the development of new organic carbonaceous semiconductors, typically, carbon quantum dots (CQDs) and graphitic carbon nitride (g-C3N4), and porphyrin small molecules and their hybrids with graphitic carbon nitride, meanwhile, their application in the field of photocatalytic solar fuel generation. In the chapter 1, a general review about background and mechanism of photocatalytic solar fuel generation are introduced first. Next, the features and developments of porphyrin and graphitic carbon nitride for the photocatalytic redox reaction are discussed. In chapter 2, the synthesis, characterization methods and photocatalytic experiment in details are described. In chapter 3, gram-scale CQDs are facilely synthesized by simple thermal treatment of citric acid monohydrate, and microporous 1D nanorods of g-C3N4 are prepared through template-free chemical approach. The photocatalytic properties of 1D protonated g-C3N4 (HCN) modified with different amount of CQDs were evaluated by the rate of H2- evolution under visible light irritation. The results demonstrate that g-C3N4/CQDs with the optimal CQDs amount of 0.25 wt.% afford the highest H2-production rate of 382 μmol h-1 g-1 with apparent quantum yield (AQY) of 1.9% which was about 3-fold of pure g- C3N4. The composite g-C3N4/CQDs show a remarkable stability against the photocorrosion within a continuous experiment period over 12h. The enhanced photocatalytic H2-production activity could be attribute to the intimate interface between CQDs and g-C3N4, which not only significantly improves the visible-light absorption, but also prolongs the lifetime of charge carriers and suppresses the recombination of photogenerated electron-hole pairs. This work showed that low-cost and metal-free CQDs could be an efficient photosensitizer to promote photocatalytic hydrogen generation. In chapter 4, we reported a new array of push-pull isomeric naphthalimide- porphyrins (ZnT(p-NI)PP) to investigate the effect of naphthalimide and molecular constitution on light driven hydrogen evolution from water splitting. These compounds were synthesized by integration of four naphthalimide moieties on meso-substituion of porphyrin macrocycle through para phenyl linker. Porphyrins were characterized by UV- Vis, Fluorescence and DFT calculations and compared with those of zinc tertapheylporphyrin (ZnTPP). When these porphyrins were employed as photocatalyst for the photocatalytic hydrogen production (PHP) with platinum co-catalyst, they delivered high hydrogen efficiency compared to that of ZnTPP. Particularly, ZnT(p-NI)PP exhibited 203 times higher hydrogen efficiency than the ZnTPP. This could be ascribed to the efficient exciton dissociation into holes and electrons at the photoexcited state of ZnT(p-NI)PP and then electrons were transferred to the proton through platinum. These results indicate that introduction of naphthalimide at meso-position of porphyrin through para phenyl linker is a versatile strategy to improve the photocatalytic hydrogen evolution of porphyrin based materials. In addition, the other two isomeric naphthalimide conjugated porphyrins through meta-and ortho-phenyl linker, ZnT(m-NI)PP and ZnT(o-NI)PP are also developed for photocatalytic H2 production. The para-linked isomer, ZnT(p-NI)PP delivered a much higher H2 production rate of 973 μmol h−1g -1 compared to that of ZnT(m-NI)PP (597 μmol h−1g −1) and ZnT(o-NI)PP (54 μmol h−1g −1), respectively. This could be attributed to the efficient intramolecular energy transfer from the naphthalimide to the porphyrin ring. In chapter 5, a series of NP/g-C3N4 hybrids of graphitic carbon nitride (g-C3N4) with naphthalimide-porphyrin (ZnT(p-NI)PP, labelled as NP) have been developed for photocatalytic hydrogen production. Planar naphthalimide-porphyrins are adsorbed onto flexible two-dimensional g-C3N4 through π-π stacking, which are characterized by scanning electronic microscopy and X-ray photoelectron spectroscopy. Except for its function as photosensitizer, NP in the hybrids could efficient inhibit the charge recombination by electron transfer for the lower lowest unoccupied molecular orbital of NP than g-C3N4, whereas facilitate energy transfer from g-C3N4 donor to NP acceptor for efficient overlap of emission spectrum of NP and absorption of g-C3N4. As a result, the hybrid containing weigh ratio of 2% NP (2%NP/g-C3N4) exhibits an enhanced photocatalytic hydrogen production rate (HPR) of 2297 μmol g−1 h −1, while pristine g- C3N4 shows a HPR of 698 μmol g−1 h −1. The 2%NP/g-C3N4 shows the best performance when compared with the reported hybrids of g-C3N4 with Zn(II) -tetrakis(4- carboxylphenyl) porphyrin (ZnTCPP/g-C3N4) and Zn(II)-tetrakis(4- hydroxyphenyl)porphyrin (ZnTHPP/g-C3N4) in photocatalytic hydrogen production under the same conditions. In the chapter 6, the future work on photocatalytic CO2 reduction, perspectives and conclusions are included

Indiana University-Purdue University Indianapolis (IUPUI) / Semiconductor nanocrystals (SNCs) are a class of material with one dimension <100 nm, which display size, shape, and composition dependent photophysical (absorption and emission) properties. Ultrasmall SNCs are a special class of SNCs whose diameter is <3.0 nm and are strongly quantum confined leading to a high surface to volume ratio. Therefore, their electronic and photophysical properties are fundamentally dictated by their surface chemistry, and as such, even a minute variation of the surface ligation can have a colossal impact on these properties. Since the development of the hot injection-method by Bawendi et al., the synthetic methods of SNCs have evolved from high-temperature, highly toxic precursors to low-temperature, relatively benign precursors over the last 25 years. Unfortunately, optimization of their synthetic methods by appropriate surface ligation is still deficient. The deficiency lies in the incomplete or inappropriate surface passivation during the synthesis and/or post-synthetic modification procedure, which due to the high surface to volume ratio of ultrasmall SNCs, is a significant problem. Currently, direct synthetic methods produce SNCs that are either soluble in an aqueous media or soluble in organic solvents therefore limiting their applicability. In addition, use of insulating ligands hinder SNCs transport properties and thus their potential application in solid state devices. Appropriate choice of surface ligation can provide 1) solubility, 2) stability, and 3) facilitate exciton delocalization. In this dissertation, the effects of appropriate surface ligation on strongly quantum confined ultrasmall SNCs was investigated. Due to their high surface to volume ratio, we are able to highly control their optical and electronic properties through surface ligand modification. Throughout this dissertation, we utilized a variety of ligands (e.g. oleylamine, cadmium benzoate, and PEGn-thiolate) in order to change the solubility of the SNC as well as investigate their optical and electronic properties. First delocalization of the excitonic wave function 1) into the ligand monolayer using metal carboxylates and 2) beyond the ligand monolayer to provide strong inter-SNC electronic coupling using poly(ethylene) glycol (PEG)-thiolate was explored. Passivation of the Se sites of metal chalcogenide SNCs by metal carboxylates provided a two-fold outcome: (1) facilitating the delocalization of exciton wave functions into ligand monolayers (through appropriate symmetry matching and energy alignment) and (2) increasing fluorescence quantum yield (through passivation of midgap trap states). An ~240 meV red-shift in absorbance was observed upon addition of Cd(O2CPh)2, as well as a ~260 meV shift in emission with an increase in PL-QY to 73%. Through a series of control experiments, as well as full reversibility of our system, we were able to conclude that the observed bathochromic shifts were the sole consequence of delocalization, not a change in size or relaxation of the inorganic core, as previously reported. Furthermore, the outstanding increase in PL-QY was found to be a product of both passivation and delocalization effects. Next we used poly(ethylene) glycol (PEG)-thiolate ligands to passivate the SNC and provide unique solubility properties in both aqueous and organic solvents as well as utilized their highly conductive nature to explore inter-SNC electronic coupling. The electronic coupling was studied: 1) as a function of SNC size where the smallest SNC exhibited the largest coupling energy (170 meV) and 2) as a function of annealing temperature, where an exceptionally large (~400 meV) coupling energy was observed. This strong electronic coupling in self-organized films could facilitate the large-scale production of highly efficient electronic materials for advanced optoelectronic device applications. Strong inter-SNC electronic coupling together with high solubility, such as that provided by PEG-thiolate-coated CdSe SNCs, can increase the stability of SNCs during solution-phase electrochemical characterization. Therefore, we utilized these properties to characterize solution-state electrochemical properties and photocatalytic activity of ternary copper indium diselenide (CuInSe2) SNCs as a function of their size and surface ligand chemistry. Electrochemical characterization of our PEG-thiolate-coated SNCs showed that the thermodynamic driving force (-ΔG) for oxygen reduction, which increased with decreasing bandgap, was a major contributor to the overall photocatalytic reaction. Additionally, phenol degradation efficiency was monitored in which the smallest diameter SNC and shortest chain length of PEG provided the highest efficiency. The information provided herein could be used to produce superior SNC photocatalysts for a variety of applications including oxidation of organic contaminants, conversion of water to hydrogen gas, and decomposition of crude oil or pesticides. Therefore, we believe our work will significantly advance quantitative electrochemical characterization of SNCs and allow for the design of highly efficient, sustainable photocatalysts resulting in economic and environmental benefits.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19000号 / 工博第4042号 / 新制||工||1622(附属図書館) / 31951 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 田中 庸裕, 教授 今堀 博, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM