Inorganic / polymeric assemblies as catalysts for water splitting

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buir.advisorKaradaş, Ferdi
dc.contributor.authorKap, Zeynep
dc.date.accessioned2018-10-03T12:47:25Z
dc.date.available2018-10-03T12:47:25Z
dc.date.copyright2018-09
dc.date.issued2018-09
dc.date.submitted2018-09-02
dc.departmentDepartment of Chemistryen_US
dc.descriptionCataloged from PDF version of article.en_US
dc.descriptionThesis (M.S.): Bilkent University, Department of Chemistry, İhsan Doğramacı Bilkent University, 2018.en_US
dc.descriptionIncludes bibliographical references. (leaves 62-72).en_US
dc.description.abstractSplitting water with sunlight is an attractive and promising research topic over the last two decades since it produces a non-carbon-based resource, hydrogen, which is a suitable energy carrier due to its high energy output and for being environmentally friendly. A great deal of research in this eld has been centered on the development of e cient water oxidation and reduction catalysts. The rst part of the thesis focuses on a novel photosensitizer-water oxidation catalyst (PS-WOC) dyad. A Ru metal coordinated pyridine-based ligand and a cobalt-iron pentacyanoferrate have been used as the photosensitizer and water oxidation catalyst, respectively. In this assembly, poly(4-vinylpyridine) serves as the bridging group between two units mainly to enhance the performance and stability of the system compared to its analogous intermolecular system. A 5-fold improvement on the catalytic activity has been achieved with a turnover frequency (TOF) of 5:6 10-4 s-1 under 1 hour light illumination and a turnover number (TON) of 11 in a 6-hour catalytic study. Evolved oxygen was quanti ed with gas chromatography. Structural characterization was carried out by Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet-Visible Spectroscopy (UV-Vis), X-Ray Photoelectron Spectroscopy (XPS), X-Ray Powder Di raction (XRD), Scanning Electron Microscopy (SEM), and Energy-dispersive X-Ray Spectroscopy (EDX) techniques. Comparative XPS and FTIR studies were performed on pristine and post-catalytic samples to con rm the stability of the dyad. In the second part of the study, a facile synthetic pathway using poly(4- vinylpyridine) as a polypyridyl platform has been reported for the formation of a cobalt-based metallopolymer. Electrochemical studies indicate that the metallopolymer acts as an e cient H2 evolution catalyst similar to cobalt-polypyridyl complexes. Furthermore, metallopolymer can be transformed to cobalt particles when a cathodic potential is applied in the presence of an acid. It has been found that these cobalt particles also serve as e cient hydrogen evolution catalysts. Approximately 80 µmoles of H2 gas can be collected during 2 h of electrolysis at -1.5 V (vs. Fc+/0) in the presence of 60 mM of acetic acid. A comprehensive study of the electrochemical and electrocatalytic behavior of cobalt-poly(4-vinylpyridine) was discussed in detail.en_US
dc.description.degreeM.S.en_US
dc.description.statementofresponsibilityby Zeynep Kap.en_US
dc.format.extentxix, 72 leaves : illustrations, charts (some color) ; 30 cm.en_US
dc.identifier.itemidB159045
dc.identifier.urihttp://hdl.handle.net/11693/48072
dc.language.isoEnglishen_US
dc.publisherBilkent Universityen_US
dc.rightsinfo:eu-repo/semantics/openAccessen_US
dc.subjectWater Reduction Catalysten_US
dc.subjectHydrogen Evolution Catalysten_US
dc.subjectLight-Driven Water Oxidation Catalysten_US
dc.subjectLight-Driven Oxygen Evolution Catalysten_US
dc.subjectDyaden_US
dc.subjectWater Splittingen_US
dc.subjectRutheniumen_US
dc.subjectPrussian Blueen_US
dc.subjectPolymeren_US
dc.titleInorganic / polymeric assemblies as catalysts for water splittingen_US
dc.title.alternativeSuyun ayrışma reaksiyonu için inorganik / polimerik yapılı katalizörleren_US
dc.typeThesisen_US

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