Artifical photosynthesis: Dye assisted photocatalytic reduction of carbon dioxide over pure and platinum containing titania

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Tezin Türü: Yüksek Lisans

Tezin Yürütüldüğü Kurum: Orta Doğu Teknik Üniversitesi, Mühendislik Fakültesi, Kimya Mühendisliği Bölümü, Türkiye

Tezin Onay Tarihi: 2005

Öğrenci: ÖZLEM ÖZCAN

Danışman: DENİZ ÜNER

Özet:

The aim of this study is to test the limits of photocatalytic reduction of CO2 over Pt and light harvesting dye promoted TiO2 films under UV and visible light. Thick and thin TiO2 film catalysts are coated onto 1 cm long glass beads via a common sol-gel procedure and dip coating technique. TiO2 thin films were promoted by Pt and three different light harvesting molecules: RuBpy (Tris (2,2̕ ا bipyridyl) ruthenium (II) chloride hexahydrate) , BrGly (1,7-dibromo-N,N̕-(t-butoxycarbonyl-methyl)-3,4:9,10-perylene-diimide) and BrAsp (1,7-dibromo-N,N̕-(S-(1-t-butoxy-carbonyl-2-t-butoxycarbonyl-methyl)-ethyl)- 3,4:9,10-perylenediimide). Their SEM, XRD, UV-Vis spectroscopy and hydrogen chemisorption characterizations are performed. Reaction tests are performed for the catalysts under UV and visible light. The only quantifiable reaction product was methane. With RuBpy containing catalysts hydrogen production was observed under UV light, but not quantified. The results indicated that Pt addition resulted in higher yields in UV experiments. The presence of light harvesting molecules resulted in increase in photocatalytic activity for thin films, whereas it resulted in no change or decrease for the thick films. The latter case may occur due to the UV filtering effect of these dyes. Use of dyes (with visible range absorption bands) as promoters made visible light excitation possible. This resulted in photocatalytic activity under visible light, which was not observed with unpromoted and Pt promoted TiO2 thin film catalysts. Under visible light methane was the only quantified photoreduction product. CO evolution was also observed, but not quantified. The photocatalytic activities of the dye promoted TiO2 were in the order of RuBpy~BrAsp>BrGly. The methane yields of visible light experiments were one order of magnitude lower than the ones under UV light.