Phd Degree / Doktora
Permanent URI for this collectionhttps://hdl.handle.net/11147/2869
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Doctoral Thesis Removal of Dyes and Antibiotics by Adsorption and Photocatalytic Degradation Using Zn-Based Composites(01. Izmir Institute of Technology, 2023) Saygı, Gizem; Çakıcıoğlu Özkan, Seher FehimeIn this study, the ZIF-8 was synthesized and immobilized on the clinoptilolite surface (ZIF8@CLN) and doped with Ag nanoparticles, forming the Ag-ZIF8 and Ag-ZIF8@CLN composite materials. The characterization results indicated that the ZIF-8 was well-deposited on the clinoptilolite surface and doped successfully with Ag nanoparticles. The adsorption and photocatalytic activity of these adsorbents/catalysts were evaluated by the removal of the organic pollutants such as dyes and antibiotics. The target dyes were cationic Methylene blue (MB), anionic Methyl orange (MO) and Congo red (CR), and zwitterionic Rhodamine B (RhB). The target antibiotic was tetracycline (TC). The influence of various parameters on removal was investigated using different initial pH, photocatalyst amount, pollutant concentrations and ionic strength. The results showed that ZIF-8 and ZIF-8@CLN are excellent adsorbents. However, the photocatalytic activity of Ag-ZIF8 and especially Ag-ZIF8@CLN composites were much better than ZIF-8 and ZIF-8@CLN for degradation of all dyes. The Ag-ZIF8 and Ag-ZIF8@CLN composite catalysts exhibited more than 90% removal capacity under UV irradiation for 120 min with the dye concentration of 25 mg L-1 at the optimum pHs of each dye. The enhanced adsorption and photocatalytic performance of the composite photocatalysts was attributed to the synergistic effect between the ZIF-8, CLN and Ag. The adsorption data were evaluated by considering adsorption isotherms, kinetics and thermodynamics using target dyes and antibiotics. Proposed photodegradation mechanism of the dyes over Ag-ZIF8@CLN was explained detailed. This work introduced the ZIF-8-based composite photocatalysts with high efficiency, and may provide to prefer these catalysts in photocatalytic field.Doctoral Thesis Development of Innovative Polymeric Membranes Using Green Approaches for Water and Energy Sustainability(01. Izmir Institute of Technology, 2022) Güngörmüş Deliismail, Elif; Altınkaya, SacideIn this thesis, innovative polymeric membranes with fast, simple, and easily scalable manufacturing procedures were developed to demonstrate the potential of membrane technology in making chemical processes more sustainable. In this scope, firstly, it was focused on minimizing the adverse chemical, environmental, and economic effects of conventional drying processes by integrating membrane technology into the production of nano/microparticles. Acid-resistant polyaniline based ultrafiltration (UF) membrane and solvent-resistant poly (ether imide sulfone) based UF membrane were developed to produce aluminum sulfate powder and silica powder, respectively. The developed high-performance and antifouling membranes made the production of powders more sustainable and environmentally friendly by enabling the recovery of the acid/solvent used in the synthesis and the reduction of energy consumption for drying. The third part of the thesis focused on biodiesel production with a high-performance, antifouling, alumina-calcium oxide catalyst-modified polyethersulfone UF membrane. Combining membrane technology with reaction engineering allowed for the elimination of the catalyst recovery step, shortened the reaction time to reach a desirable yield, and reduced energy consumption, resulting in more sustainable biodiesel production than existing production techniques. In the last part of the thesis, a high-performance, antibiofouling/antibacterial citric acid doped polyaniline based UF membrane was developed. Ensuring sustainability improvement in membrane production in all applications was the main objective of this thesis. By reducing the number of steps in membrane production, the amount of wastewater generated, and toxic waste released during membrane production was minimized, and energy consumption was significantly reduced.Doctoral Thesis Heat and Mass Transfer Characteristics of Adsorbents in Heat Pump and Refrigerator(01. Izmir Institute of Technology, 2023) Gündoğan, Şefika Çağla; Çakıcıoğlu Özkan, Seher FehimeDue to increasing drought, pandemic and climate crisis in recent years, researchers have increased their studies on environmentally friendly energy use. Although there are technological developments in the production of energy from renewable energy sources, the storage of this produced energy is still a problem that awaits a solution. At this point, adsorption heat pumps with high primary energy efficiency come to the fore as a developing technology and attract the attention of researchers. However, low heat transfer properties in the adsorbent bed reduce the performance of adsorption heat pumps and limit their applications. The aim of this thesis was to improve the performance of the adsorption heat pump by increasing the effective thermal conductivity within the adsorbent bed. Two methods have been employed to enhance the effective thermal conductivity. In the first method, which was unconsolidated adsorbent bed design, it was aimed to increase the thermal conductivity of the bed with metal additives with a continuous structure. In the second method, which is known as consolidated bed design, the effective thermal conductivity of zeolite 13X was tried to be enhance with a high conductive material, reduced graphene oxide. In the experimental studies, it was observed that the thermal conductivity increased from 0.12 W/m.K to 0.28 W/m.K in unconsolidated bed design by means of fin-shaped metal additive. In consolidated adsorbent bed design, the effective thermal conductivity of the Graphene/Zeolite 13X (1 wt% Graphene) was determined as 0.1613 W/m.K. In theoretical studies, the effect of thermal conductivity in the temperature, pressure and adsorbate concentration was investigated. The indirect and direct effects of effective thermal conductivity on specific cooling/heating power (SCP/SHP) and coefficient of performance (COP) values were examined. Although the effect of thermal conductivity on COP was ignored in most of the studies in the literature, it was observed that COP increased from 0.01 to 0.10 when thermal conductivity increased from 0.12 W/m.K to 1 W/m.K.Doctoral Thesis The Valorization of Various Wastewater for Hydrogen Production by Photocatalytic Oxidation(01. Izmir Institute of Technology, 2021) Orak, Ceren; Yüksel Özşen, AslıHydrogen is a clean, green and sustainable energy and photocatalysis a better approach for hydrogen production from various wastewaters. It was aimed to evolve new hybrid solar-driven catalysts for photocatalytic hydrogen production from various wastewaters. Firstly, catalysts were synthesized. Their characterization study were performed and PL results show that the most promising catalyst was GLFO. The impacts of pH, catalyst loading and light over hydrogen production from SMS were investigated using all synthesized catalysts. The hybrid catalysts show higher efficiency. FFD was created to elucidate the impacts of reaction parameters and graphene content of catalyst had a major impact. To optimize the reaction parameters for all hybrid catalysts, an experimental matrix was created using BBD. The higher hydrogen amounts were observed using GLFO. The same experimental matrix was used to search the effects of reaction parameters over produced hydrogen amounts from sugar beet wastewater using all hybrid catalysts and the highest hydrogen production was observed using GLFO. The observed reaction followed first order reaction model based on TOC removal. Therefore, the degradation of organic pollutants in wastewater streams and hydrogen evolution could simultaneously be achieved. Same experimental matrix was also used for hydrogen evolution from DBU using all hybrid catalysts. Relatively lower hydrogen amounts were obtained so that it was also treated under subcritical conditions. FFD was created to search the impacts of reaction parameters and NaOH concentration and current density had an impact over DBU removal. Based on GC-MS results, the hazardous intermediates did not form during hydrothermal electrolysis.Doctoral Thesis Development of Antifouling Nanofiltration and Antibiofouling Ultrafiltration Polymeric Membranes Using Facile Protocols(Izmir Institute of Technology, 2021) Cihanoğlu, Aydın; Altınkaya, Sacide; Şeker, ErolOne of the major goals in membrane separation technology is to develop fouling-resistant membranes that can provide a long operating time and low operation costs. This thesis aims to manufacture fouling and biofouling-resistant polymeric nanofiltration (NF) and ultrafiltration (UF) membranes using unique approaches. The first approach was to change coagulation bath composition in the phase inversion technique for manufacturing fouling-resistant polyamide-imide (PAI) based NF and biofouling-resistant polysulfone (PSF)/sulfonated polyethersulfone (PSF-SPES) based UF membranes. To this end, hydrophilic branched polyethyleneimine (PEI) dissolved in the coagulation bath allowed the preparation of a positively charged PAI based NF membrane by forming a covalent bond with the imide group in the PAI. To manufacture antibacterial UF membranes, a strong antibacterial surfactant, cetyltrimethylammonium bromide (CTAB), was dissolved in the coagulation bath and made an electrostatic interaction with SPES at the polymer/bath interface during phase inversion. Both membranes were prepared in a one-step process without using any pore formers in the casting solution. The second approach used in the thesis focused on modification of commercial polyethersulfone (PES) UF membranes with co-deposition of dopamine and CTAB molecules to impart antibiofouling behavior without compromising the pore size and pure water flux of the support. To achieve this task, during modification, an inert physical barrier was created inside the membrane pores by continuously feeding nitrogen gas (N2) from the backside of the support to prevent pore penetration. In the last approach, ultrasound as a green, controllable trigger was used for modifying PSF and PSF-SPES UF membranes with dopamine. The main purpose of using ultrasound was to accelerate the polymerization kinetics of dopamine, hence shortening the modification time.Doctoral Thesis Development of a Plasmonic Biosensor for Detection of Exosomes(Izmir Institute of Technology, 2020) Taykoz, Damla; Bulmuş Zareie, Esma Volga; Tekin, Hüseyin CumhurThe aim of this work was to develop Localized Surface Plasmon Resonance (LSPR) surfaces for quantitative detection of exosomes from different sources. For this aim, gold nanorods (AuNRs) with a mean diameter of 40 nm with an aspect ratio of 2.9 were first synthesized and characterized. The self-assembly of AuNRs on glass wafers were optimized through several experiments. In parallel, PEGylation of cetrimonium bromide (CTAB) stabilized AuNRs was investigated using PEGs with three different molecular weights via LSPR, zeta potential and XPS techniques. PEGylated AuNRs were further self-assembled on silanized microscope slides as confirmed. Surface functionalization of AuNR patterned slides was performed using alkane thiol molecules having carboxylic acid and hydroxyl functional groups and confirmed via XPS, FTIR and zeta potential. Specific antibodies (Ab) were conjugated to the surface following two different methods, i.e. click and NHS/EDC chemistry. To perform click chemistry strategy, ImmuneLink® molecules were conjugated with Abs and the final conjugate was used to functionalize surfaces prepared beforehand using azide bearing molecules. The functionalization procedure was confirmed via XPS FTIR and LSPR spectroscopy. The orientation of the antibodies on the AuNRs patterned surfaces was investigated with LSPR in comparison with conventional EDC/NHS chemistry. The click-chemistry strategy proved to provide conjugation of antibodies through their Fc regions exposing Fab regions better for antigen recognition. Finally, surfaces functionalized with a variety of antibodies were used to detect first a pregnancy-associated protein, PLAP, and then exosomes obtained from human semen samples with pre-determined exosome concentrations. The LoD of the biosensor surfaces was found to be between 103-104 exosomes/mL and 5 ng/mL (0.3 pM) PLAP. Human breast cancer cell culture samples having an unknown concentration of exosomes were further analyzed using the newly developed LSPR biochips and the exosome concentration was determined as 108 exosomes/mL for MCF-7 cell line and 107 exosomes/mL for MDA-MB-231 cell line.Doctoral Thesis Biofuels and Biochemicals Production From Microalgae Over Solid Catalysts(Izmir Institute of Technology, 2020) Deliismail, Özgün; Şeker, ErolThe target of this study was the investigation of biofuel and/or biochemical production from microalgae in growth medium or its lipids over heterogenous catalyst. The primary aim was to study the conversion of 6 wt. % N. Oculata into biofuels without harvesting and dewatering over Ni-Al2O3-SiO2 catalyst at 80oC and 1 atm for 24 h. Solgel method was used to synthesize the catalyst by using the acids of H2SO4, HCl, and HNO3 to investigate the effect of acid type on catalytic activity. The catalyst prepared with H2SO4 yielded the highest conversion. The treatment of the catalyst prepared by H2SO4, with NaCl increased the conversion from 74 % to 91.5 % under same reaction conditions. The products included poly- or monosaccharides, esters and fatty acids. To achieve this conversion, Ni presence was significant beside total acidity of 25 µmol per gram of catalyst, and acidic strength ranging between 130-380oC. A new industrial application was proposed for direct conversion of 6 wt. % N. Oculata into biofuels at 80oC and 1 atm. The capacity of the plant was 1669 liters biofuel per year from 1064 liters microalgae solution per hour. The catalyst prepared with H2SO4 was used to coat either inner surface of tubes or 1-meter pluggable monoliths in tubular reactor having 20 m length and 1000 tubes each of which had 4 cm diameter. The microalgae solution was heated with Therminol®66 heated via parabolic troughs. For operation continuity, ~46000 kg of oil was stored in the tank at 120 o C for 12 h. The production of ethyl ester biodiesel from Spirulina sp. and N. Oculata lipids over 60 % CaO/Al2O3 was studied at 50oC and 1 atm. Ethanol: lipid molar ratio, catalyst amount and reaction time were investigated parameters to identify their effects on catalytic activity. The study showed that ~59 % biodiesel yield was obtained in the presence of the catalyst which was 6 wt. % of lipids, in 30 min. at ethanol: lipid molar ratio of 12 while 90 %-99 % yield was acquired at ethanol: lipid molar ratios of 24 and 48. To achieve these yields, weak basic strength in the form of bicarbonate was necessary while high basicity was not essential. Pure alumina and CaO did not yield any lipid conversion. Glycerolysis of triacylglycerol took place in series with reverse transesterification of triacylglycerol at catalyst amount which was 6 wt. % of lipids, ethanol: lipid molar ratio of 24 and 48, and 60 min. reaction time.Doctoral Thesis Development of Chitosan Based Biofoams(Izmir Institute of Technology, 2020) Olcay Kurt, Aybike Nil; Polat, Mehmet; Polat, Hürriyet; Polat, Mehmet; Polat, HürriyetChitosan is a preferred bio-foam material used in many research fields such as tissue engineering and drug delivery due to its unique structural features (wide pH stability, nontoxic-biocompatible-biodegradable, anti-inflammatory, antimicrobial). However, chitosan foams are mechanically too weak to maintain the desired shape until newly formed tissue natures. A wound infection and serious tissue necrosis, endanger human's lives. So, a dressing is required to protect loss of fluids and proteins from the wound area and prevents any bacterial invasion replacing the function of skin temporarily. Therefore controlled drug release from a wound dressing is necessary with a biocompatibility and enough mechanical strength. The aim of this study was the synthesis of mechanically durable - dual porosity chitosan bio-foams to provide a controlled drug release. For this purpose, oil droplets formed in a chitosan solution were used as templates to produce micropores that also contain vancomycin (a model antibiotic-hydrophylic) and curcumin (a model anti-inflammatory-hydrophobic) in the walls of the chitosan matrix with large structural voids. An anionic surfactant, sodium dodecyl sulfate (SDS) alone, was used as a crosslinking agent which was a new approach. Then the structures were characterized by SEM, FTIR, mechanical tests and BET analysis. The chitosan foams have dual pore structures. 1) The intrinsic micro pores that the walls of chitosan matrix have with different morphology that depends on the oil phase. 2) The structural voids that the chitosan matrix have, present even in the absence of an oil phase that depends on the experimental conditions. The mechanical strength of the foams were found to be much higher (up to 250 kPa) compare to the foams produced in literature and suggested to be suitable to use for wound dressing applications. The drug release mechanism of foams were found to depend on the conditions used for foam development and the released kinetics were presented with a mathematical model.Doctoral Thesis Catalytic Conversion of Glucose To Alkyl Glucosides(Izmir Institute of Technology, 2020) Mutlu, Vahide Nuran; Yılmaz, SelahattinIn this study, it was pursued to develop acidic mesoporous catalysts for the synthesis of octyl glucosides. Butyl glucoside synthesis was used for catalyst screening. Tungstophosphoric acid (TPA) incorporated mesoporous silica (TPA-SBA-15), sulfated La incorporated titania-silica (SO4/La-TiO2-SiO2), organosulfonic acid functionalized mesoporous silica (Propyl-SO3-SBA-15), and sulfated mesoporous carbon (SO4/CMK-3) catalysts were prepared for this purpose. The effects of the active species (sulfates, tungstophosphoric acid and organosulfonic acid) and promoter (La) on the catalyst properties and activity were investigated. All the catalysts had mesoporous structure and high surface area. The acidity and acid site character varied depending on the catalyst type and amount of the active sites. La promoter was found effective to enhance the sulfation performance and to improve the stability of sulfates. The TPA-SBA-15 catalysts provided high glucose conversions (over 99%) and butyl glucoside yields (over 95%) due to their acidity, Keggin ion structure and pore size. The SO4/La-TiO2-SiO2 catalysts and SO4/CMK-3 catalysts were also active with glucose conversions of 74.4 % and 70 % respectively. The reaction parameters such as the reaction temperature (117 and 100 oC) and catalyst amount (20 and 30 wt% wrt. glucose) were studied in butyl glucoside synthesis over TPA-SBA-15 and SO4/La-TiO2-SiO2 which were the most active catalysts. These catalysts were found to be reusable in glycosidation with 1-butanol. Octyl glucoside synthesis was carried out via direct glycosidation. The octyl glucoside yields obtained over TPA-SBA-15 and SO4/La-TiO2-SiO2 catalysts were above 55 % and 43 % respectively. The catalysts were found promising for further investigations.Doctoral Thesis An In-Depth Study of Nucleation and Growth Processes During Stöber Silica Synthesis(Izmir Institute of Technology, 2019) Sop, Elif Suna; Polat, MehmetSilica nanoparticles (SNPs) which can be synthesized with high surface area, controllable morphology and desired particle size have gained significant interests in high-end applications such as catalysis, chemical sensors, cosmetics and drug delivery applications. The sol-gel technique is the most commonly applied method for manufacturing these particles owing to its simplicity and suitability for allowing surface modifications to the final product. Though monodisperse amorphous SNPs have been studied extensively, how their formation proceeds through nucleation and growth is still a topic of debate. Over the years, a number of mathematical models have been suggested for the nucleation and growth of SNPs; some suggesting that silica growth occurred through monomer addition while some arguing that aggregation of nuclei/subparticles were the dominant mechanism. Nevertheless, a clear understanding of the nucleation and growth sub-processes is extremely important in control on the size and shape of SNPs for those industrial applications which demand specific morphology and surface properties. The need for a simple, robust and generalized model, both conceptually and mathematically, to understand formation and growth of Stöber silica particles has been the main driving force for this thesis. In this study, silica synthesis was carried out under a wide variety of experimental conditions while determining the size distributions of the formed particles kinetically during different stages of the synthesis in-situ through SEM analysis using an image analysis software. The outcome of the extensive synthesis work was to obtain a clear understanding of how the formation and growth of the silica particles proceed during synthesis. This conceptual understanding of the nucleation and growth processes was then translated into a mathematical model to predict the size of the particles as a function of synthesis time.
