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Title: Visible light response semiconductor nanomaterials for heterogeneous photocatalysis in liquid phase
Author: Nagy, Dávidné
ISNI:       0000 0004 7429 8612
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2018
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The development of sustainable and green technologies powered by renewable energy sources is highly desired to address the growing global energy need and water scarcity problems. Heterogeneous photocatalysis emerged in the past decades as promising solar-powered technology for environmental remediation applications such as wastewater treatment. The photoactivity of the materials is believed to be governed by complex mechanisms, still it was shown that it may be critically dependent on the following material properties (i) ability and effectiveness to absorb incident photons, (ii) charge separation efficiency, (iii) charge utilization efficiency, (iv) morphology including the size and shape of the nanostructure and its distribution and (v) the crystal structure, phase composition and crystallinity ... etc. Hence, most strategies aiming to improve the performance of photocatalytic materials may focus on one or more of the aforementioned aspects. Beside developing new materials or modifying existing systems, the development of sustainable, easy-to-operate systems are highly desired for developing countries such as Africa where almost half of the population are affected by water scarcity of some sort. For this motivation the immobilization of powder catalyst could be one attractive solution. In this thesis three experimental systems are presented. In the first two the effect of material properties on the photoactivity whereas in the third chapter the immobilization of powder catalyst was investigated. The first experimental project aimed to study the effect of synthesis parameters of WO3 nanostructures on its morphology, phase composition, optical properties and ultimately on the photoactivity. Understanding the role of process parameters to gain control over the material properties is still a challenge but is of great interest in photocatalysis. Here, a hydrothermal synthesis method was employed to synthesize WO3 nanostructures with various morphologies, crystal phases and optical properties. The effect of the solution pH, the polymeric surface modulator and the added EtOH was investigated on the material properties and on the photocatalytic activities. It was found that the crystal structure and the morphology of WO3 was influenced by the solution pH in the first place. It was proposed that stabilization effects between the crystal phase and the morphology could also influence the crystallization process beside supersaturation. It was revealed that despite the highest surface area of W-2.01-P20E, reduced oxidation state did not promote high photo-response. Instead the photoactivity of WO3 was seen as the compromise of the material properties including the optical, structural properties and the oxidation state. In the second experimental project the effect of Ag co-catalysis was studied on TiO2- Cu2O heterostructure formation. Coupling a wide band gap (TiO2) and a narrow band gap (Cu2O) semiconductor could benefit from extended light absorption properties and additionally from enhanced charged separation. In this study a facile wet chemical synthesis method was coupled with a UV treatment step to fabricate TiO2-Ag-CuxO ternary hybrid nano-materials. The effect of the Ag loading (1-5%) and the synthesis sequence of the Ag deposition step was evaluated on the material properties as well as on the visible photocatalytic activity. It was revealed that both the amount and the order of the Ag-deposition altered the material properties considerably. Typically TiO2/CuxO/Ag (TCA) catalysts had better visible light absorption properties but reduced affinity to adsorb methyl orange (MO) to their surface. Whereas, TiO2/Ag/CuxO (TAC) catalysts in general had better dye adsorption properties relative to TCA and had more efficient decoloration properties under visible light. TOC and HPLC-MS analysis revealed that MO and possibly its degradation products were mainly mineralized and/or adsorbed to the surface of TAC catalyst with 5% nominal Ag content in the visible process generating limited amount of byproducts in the final solution. The third experimental project focused on the immobilization of the previously prepared powder TiO2-Cu2O nanostructure. In this work a fluorine-doped tin oxide (FTO) glass sheet was used as a substrate and the doctor-blade coating technique has been employed to make TiO2-Cu2O thin films. Although this technique has a widespread use in the fabrication of solar cells to the best of our knowledge this is the first report on supported TiO2-Cu2O photocatalytic systems prepared by this method. To optimize the performance of the TiO2- Cu2O thin film under visible light irradiation, the chemical composition of the doctor-blading paste and the temperature of the final thermal treatment step was studied. It was found that both the paste composition and the heat treatment step played an important role in the material properties. When the film contained ethyl cellulose the minimum temperature to remove organic additives was 350 °C. Whereas for the films containing only alpha terpineol 300 °C was sufficient. It was revealed that the higher temperature treatment resulted in more oxidized films which were also shown in their deeper colour. The most effective film under visible light irradiation was TC-0-300 which contained no cellulose and was treated at the lowest temperature.
Supervisor: Ferrari, Maria-Chiara ; Brandani, Stefano Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: material science ; photocatalysis ; purification of wastewater ; WO3