M.Sc. (Chemistry) / Please refer to full text to view abstract

Titanium oxide has found different applications in environmental pollution remediation through its use as a photocatalyst for the purification of air and water. However, despite many advantages of TiO2, its use in unmodified form for photocatalytic reactions is hampered by a number of inherent physicochemical properties. The research in this thesis shows that TiO2 containing either copper (Cu) alone or combined copper-activated carbon (Cu-AC) are active in the simultaneous photocatalytic remediation of nitrate and oxalic acid, while pure titania and titania-activated carbon (TiO2/AC) composites found inactive for the reaction. In the case of photocatalytic removal of phenol, titania-thermally reduced graphene oxide (TiO2-TGO) exhibited superior photocatalytic performance than titania-graphene oxide (TiO2-GO) and pure TiO2.

Photocatalytic water splitting using solar irradiation has the potential to produce sustainable hydrogen fuel on a large scale. Practical solar energy conversion requires the development of new, stable photocatalysts that operate efficiently under a broad range of visible wavelengths. Organic semiconductors are increasingly being employed as photocatalysts due to their earth abundance, aqueous stability, and optical absorptions that can be tuned to the solar spectrum. However, much remains unknown about the mechanism of organic semiconductor photocatalysis, and significant efficiency improvements need to be made before organic photocatalysts can achieve practical solar energy conversion. In chapter 2 the effect of residual Pd on hydrogen evolution activity in conjugated polymer photocatalysts was systematically investigated using colloidal poly(9,9- dioctylfluorene-alt-benzothiadiazole) (F8BT) nanoparticles (NPs). Residual Pd, originating from the synthesis of F8BT via Pd catalysed polycondensation polymerisation, was observed in the form of homogenously distributed Pd NPs within the polymer. Residual Pd was essential for any hydrogen evolution to be observed from this polymer, and very low Pd concentrations (<40 ppm) were sufficient to have a significant effect on the hydrogen evolution reaction (HER) rate. The HER rate increased linearly with increasing Pd concentration from <1 ppm to approximately 100 ppm, at which point the rate began to saturate. Transient absorption spectroscopy experiments support these conclusions and suggest that residual Pd mediates electron transfer from the F8BT NPs to protons in the aqueous phase. Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. In chapter 3 we demonstrate that incorporating a heterojunction between a donor polymer and non-fullerene acceptor in organic NPs can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core-shell structure to an intermixed donor/acceptor blend, and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmolh-1g -1 under 350 to 800 nm illumination and external quantum efficiencies over 6% in the region of maximum solar photon flux.

Converting solar energy into useful chemical bonds via photocatalysis is a growing field aimed at addressing global challenges. The research disclosed describes heterogeneous photocatalysis as a nanophotoelectrochemical cell as photocatalysts enable both reduction and oxidation reactions using the local charge separation of photo-excited carriers. Herein, experimental and theoretical results of nanoscale electrolysis of water on the surface of CrOx/Pt/SrTiO3 showed that ohmic losses are negligible when the anode and cathode are within nanometer distances from each other. Additionally, increasing the photocatalytic rate of water splitting by increasing the light intensity demonstrated that pH gradients can still form at the nanoscale. These pH gradients can be minimized by the incorporation of buffers. Typically, photocatalysts decorated with noble-metal nanoparticles can be used for overall water splitting, but generally suffer from low yields due to the water-forming back reaction. The unwanted water-forming back reaction was successfully suppressed by coating Pt nanoparticles on the surface of SrTiO3 with a 2nm CrOx layer that block O2 gas from reaching the surface of the Pt nanoparticle. The back reaction can also be suppressed without the use of a protective layer material by changing the intrinsic nature of the Pt nanoparticle from a metallic state to an oxidized state. The Pt nanoparticles were able to maintain an oxidized state by reducing the particle size below 2 nm. Oxidized Pt particles are less likely to bind to H2, O2, and CO gas, unlike metallic Pt, thereby making it selective for hydrogen generation. Finally, CdS was found to be perform the direct trifluoromethylation of heteroarenes in a single step as opposed to the current multi-step synthetic procedures. The trifluoromethylation of organic compounds is relevant to the field of medicinal chemistry for the synthesis of pharmaceutical drugs. By improving overall water splitting via photocatalysis significantly, artificial photosynthesis may be achieved leading to a solution to the global energy security dilemma. By improving photoredox catalysis of organic compounds via photocatalysis, high value organic compounds (such as pharmaceuticals) can be synthesized more readily under milder conditions.

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Στην παρούσα διατριβή ειδίκευσης παρασκευάστηκαν πέντε νανοσύνθετα υλικά διοξειδίου του τιτανίου (στη μορφή του ανατάση) – αλλοϋσίτη σε αναλογίες 60:40, 70:30, 75:25, 80:20, 85:15 αντίστοιχα, για την περιγραφή και μελέτη των νέων βελτιωμένων χαρακτηριστικών τους και την εφαρμογή τους ως φωτοκαταλύτες στη διάσπαση αέριων ρύπων. Τα νανοσύνθετα παρήχθησαν με τη μέθοδο κολλοειδούς διαλύματος σε πήκτωμα (sol-gel) χρησιμοποιώντας αλκοξείδιο του τιτανίου (Ti(OC3H7)4) σαν διάλυμα διασποράς-επικάθισης. Οι ιδιότητες του φυσικού δείγματος αλλοϋσίτη (από τις Η.Π.Α.), καθώς επίσης και των τροποποιημένων δειγμάτων, χαρακτηρίστηκαν με τις τεχνικές περιθλασιμετρίας ακτινών Χ (XRD), υπέρυθρης φασματοσκοπίας μετασχηματισμού κατά Fourier (FTIR-ATR), ηλεκτρονικής μικροσκοπίας σάρωσης (SEM) και μέτρησης πορώδους και ειδικής επιφάνειας (BET). Επιτεύχθηκε η διασπορά των νανοσωματιδίων (3-10nm) του διοξειδίου του τιτανίου στην επιφάνεια του αλλοϋσίτη και τα αποτελέσματα της υπέρυθρης φασματοσκοπίας έδειξαν την δημιουργία δεσμών υδρογόνου μεταξύ τους. Τα τροποποιημένα δείγματα έδειξαν αύξηση της ειδικής τους επιφάνειας συγκριτικά με το φυσικό δείγμα και μεσοπορώδη δομή (5,7nm). Η μακροπορώδης δομή του αλλοϋσίτη (εσωτερικό κενό των επιμήκων κρυστάλλων) δεν ανιχνεύτηκε στα νανοσύνθετα διότι καλύφθηκε, εν μέρει, από τα νανοσωματίδια του TiO2 με αποτέλεσμα να προκύψει ένα υλικό με μικρότερο μέγεθος πόρων. Όλα τα νανοσύνθετα (και τα πέντε) έδειξαν ικανοποιητικά αποτελέσματα ως προς τη φωτοκαταλυτική τους ικανότητα στη διάσπαση αέριων ρύπων υπό την επίδραση φωτός του ορατού φάσματος αλλά και υπεριώδους ακτινοβολίας σε σύγκριση με τα αποτελέσματα που έδωσε το πρότυπο TiO2 P25. Όσον αφορά τα οξείδια του αζώτου, υπό την επίδραση της ορατής ακτινοβολίας, το νανοσύνθετο διοξειδίου του τιτανίου - αλλοϋσίτη σε αναλογία 70:30, συγκριτικά με το πρότυπο TiO2 P25, έδειξε 16,6 φορές καλύτερα αποτελέσματα ενώ υπό την υπεριώδη ακτινοβολία η φωτοκαταλυτική του ικανότητα ήταν μεγαλύτερη κατά 1,83 φορές. Στο τολουόλιο 4,8 φορές καλύτερα αποτελέσματα έδειξε το νανοσύνθετο με αναλογία 75:25. Η αυξημένη φωτοκαταλυτική δράση των νανοσύνθετων σε σχέση με τον πρότυπο φωτοκαταλύτη οφείλεται κυρίως στην καλή διασπορά των ννοκρυστάλλων ανατάση στις επιφάνειες του αλλοϋσίτη. / Five TiO2-halloysite nanocomposites (Ti-Hall 60:40, 70:30, 75:25, 80:20, 85:15) were prepared by depositing TiO2, in the form of anatase, on the halloysite surfaces using titanium isopropoxide under hydrothermal treatment at 180˚C. The nanocomposites were characterized by X-Ray diffraction (XRD), attenuated total reflection using Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM) and N2 specific surface area (SSA) analysis by BET method. Good dispersion of 3-10nm TiO2 particles on halloysite external surfaces was achieved in the TiO2- halloysite nanocomposites and ATR-FTIR results showed the formation of hydrogen bonding between TiO2 and the outer surfaces of halloysite tubes. After treating with TiO2, the nanocomposites largely showed interparticle mesopores of about 5.7nm. However, the macropores of halloysite (lumen or central hole in halloysite tubes) were not detected as a result of plugging of the lumens in halloysite tubes by TiO2 nanoparticles, at least partially. These nanocomposites were tested for their photocatalytic activities in decomposing NOX gas under visible-light irradiation and UV-visible light irradiation compared to that of the standard commercial titania photocatalyst, P25. Generally the nanocomposites showed significantly increased photocatalytic activities, while the most effective nanocomposite in decomposing NOX gas was the Ti-Hall 70:30 (16.6 and 1.83 times in visible light and UV respectively) and for tolouene the Ti-Hall 75:25 (4.8 times) compared to the commercial titania. The enhanced photocatalytic activities observed in the nanocomposites are a result of the good dispersion of the TiO2 nanocrystals on the surface of the halloysite.

Efficiency of particulate semiconductors for driving photocatalytic reactions is impractically low due to the recombination of excited carriers and intermediate species at the interface. In the literature it has been demonstrated internal depolarisation fields in ferroelectric materials separate electron and hole carriers, this gives rise to spatially distinct reduction and oxidation processes. It is hypothesised this property can supress the rate of back reactions and carrier recombination to improve photocatalytic efficiency. In this thesis the properties of ferroelectric particulates for driving photocatalytic reactions are investigated. Lithium niobate and barium titanate powders were suspended in aqueous solutions of acid black 1 or rhodamine b dye. Adsorption studies compared retention of dye in the double layer by the different powders. Under UV or simulated solar illumination barium titanate or lithium niobate powders photocatalytically decolourised the dye solutions. Powders of lithium niobate powder doped with magnesium or iron showed altered reaction rates and structural selectivity of decolourisation reactions. Photochemical deposition of silver nanoparticles at the surface of the barium titanate or lithium niobate powders increased the rate of photocatalytic decolourisation of rhodamine b solutions under UV or simulated solar illumination. Photochemical reduction of carbon dioxide to form formic acid and formaldehyde over lithium niobate powder was studied under UV illumination. Solid-liquid phase reactions were carried out using aqueous suspensions of powder bubbled with carbon dioxide gas. Solid-gas phase reactions were investigated using a purpose built reaction vessels loaded with carbon dioxide gas and water vapour. Under solid-gas phase conditions the rate of formation of products over lithium niobate powder was greater than over titanium dioxide powder.

Due to an increase of human activity, an increase health risk has emerged from the presence of pollutants in the environment. In the transition to renewable and sustainable life style, treatment of pollutants could support the shifting societies. A motivation behind material research for environmental applications is to maximize the efficiency of the materials to alleviate environmental pollution. In the case of titania, an increase of ultra-violet light absorption is needed to overcome its bandgap to produce reactive radicals, which is the basis for photocatalysis. It has been hypothesized that photonic crystal can enhance titania photocatalysis. They are structures made of at least two dielectrics with a high refractive index contrast, ordered in a periodic fashion. For a strong contrast, photonic band gaps emerge. The effect of the photonic band gap is to force complete reflection of the incoming light within its range and multiple internal reflections at its edges. By combining photonic and electronic band gap positions, it is possible to increase the absorption at the photonic band gap edges. In this thesis, fabrication method and structural analysis of titania and alumina/titania photonic structures were presented. A thorough optical analysis was performed at all steps of fabrication – beyond what previously has been reported. The photocatalytic activity was measured with two setups. Fourier Transform Infrared spectroscopy combined with arc lamps and bandpass filters was used to monitor the degradation of stearic acid in ambient air. A home-built setup was used to degrade methylene blue in solution with ultra-violet illumination. The results in this thesis show in general no correlation of the photocatalytic activity to the photonic band gap position, even though absorbance data displayed an increase absorption in this energy range. A more controlled environment might show the effect of the structure, as seen in some of the experiments.

Over the past decade, heterogeneous photocatalysis have gained lots of interest and attention among the organic chemistry community due to its applicability as an alternative to its homogeneous counterpart. Heterogeneous catalysis offers the advantages of easy separation and reusability of the catalyst. Several studies showed that under optimized conditions, efficient and highly selective catalytic systems could be developed using supported metal/metal oxide nanoparticles. In this dissertation, we summarize the progress in the development of supported palladium nanoparticles for different types of organic reactions. Palladium-decorated TiO2 is a moisture, air-tolerant, and versatile catalyst. The direct excitation of Pd nanoparticles selectively isomerized the benzyl-substituted alkenes to phenyl-substituted alkenes (E-isomer) with complete conversion over Pd@TiO2 under H2-free conditions. Likewise, light excited Pd nanoparticles catalyzed Sonogashira coupling, a C-C coupling reaction between different aryl iodides and acetylenes under very mild conditions in short reaction times. On the other hand, UV irradiation of Pd@TiO2 in alcoholic solutions promotes alkenes hydrogenation at room temperature under Argon. Thus, The photocatalytic activity of Pd@TiO2 can be easily tuned by changing the irradiation wavelength. Nevertheless, some of these systems suffer from catalyst deactivation, one of the main challenges faced in heterogeneous catalysis that decreases the reusability potential of the materials. In order to overcome this problem, we developed an innovative method called “Catalytic Farming”. Our reactivation strategy is based on the crop rotation system used in agriculture. Thus, alternating different catalytic reactions using the same catalyst can reactivate the catalyst surface by restoring its oxidation states and extend the catalyst lifetime along with its selectivity and efficiency. In this work, the rotation strategy is illustrated by Sonogashira coupling –problem reaction that depletes the catalyst– and Ullmann homocoupling –plausible recovery reaction that restores the oxidation state of the catalyst (Pd@TiO2). The selection of the reactions in this approach is based on mechanistic studies that include the role of the solvent and evaluation of the palladium oxidation state after each reaction. In a more exploratory analysis, we successfully demonstrated that Pd nanoparticles could be supported in a wide range of materials, including inert ones such as nanodiamonds or glass fibers. The study of the action spectrum shows that direct excitation of the Pd nanoparticles is a requisite for Sonogashira coupling reactions. The main advantages of heterogeneous catalysis compared to its homogeneous counterpart are easy separation and reusability of the catalyst. Finally in order to facilitate catalyst separation from batch reaction and develop a suitable catalytic system for continuous flow chemistry, we employed glass fibers as catalyst support for a wide variety of thermal and photochemical organic reactions including C-C coupling, dehalogenation and cycloaddition. Different metal/metal oxide nanoparticles, namely Pd, Co, Cu, Au, and Ru were deposited on glass wool and fully characterized. As a proof of concept, Pd decorated glass fibers were employed in heterogeneous flow photocatalysis for Sonogashira coupling and reductive de-halogenation of aryl iodides.