Design, Synthesis And Application Of Metal Organic Framework (MOF) Containing Ruthenium Complex Photosensitizer

The study of visible light-driven chemical reactions,especially photocatalysis,has made great progress in the past decades from all major branches of chemistry with the emphasis on fundamental knowledge as well as practical application.The photosynthesis system of nature utilizes sun light to drive the complex process of carbohydrate generation using water and CO₂ as the raw materials.Operating a similar photosynthesis process in an artificial system is a promising approach for the successful solar energy utilization of our world.In such a way,solar energy converts to chemical energy and is stored in the formed of chemical bonds.Meanwhile,cotemporary chemists maintain widely interest and have been spending great endeavor on the research of photo-decomposition organic contaminates in water,photo-reforming of fossil fuel,photo-promoted fine chemical synthesis,and photo-dynamic/thermal therapy et al.The content of this thesis is about synthesizing novel ruthenium sensitizer-incorporated metal organic frameworks（MOF）and exploring their application in photocatalysis,including the following four aspects:（1）Design and syntheses of novel bisterpyridine ruthenium photosensitizers substituted with two carboxylate([Ru^Ⅱ（tpyCOO^-）₂]),three carboxylate([Ru^Ⅱ（tpyCOO^-）（tpy（COO^-）₂）]^-),and four carboxylate([Ru^Ⅱ（tpy（COO^-）₂）]^2-)groups as linkers of metal organic frameworks.（2）Design and syntheses of novel two-dimensional MOF layers with[Ru^Ⅱ（tpyCOO^-）₂]as linkers and 3d transition metal（Mn,Co,Ni,Zn）as nodes.The photocatalytic hydrogen evolution reaction（HER）by the MOF layers has been studied with respect to the catalytic performance as well as catalytic mechanism.（3）Design and syntheses of novel MOF with[Ru^Ⅱ（tpyCOO^-）₂]as linkers and rare earth metal（Sm,Eu,Tb,Dy,Er,Yb）as nodes.Photocatalytic degradation of organic dyesby the Tb MOF has been studied.（4）Design and synthesis of novel MOF,Cu-MOF-Ru（tpyCOO）₂（Cu-Ru）,with[RuII（tpyCOO^-）₂]as linkers and Cu²⁺as the node,and preliminary study of photocatalytic HER performance of the copper MOF.