Synthesis And Catalytic Properties Of Ru Ions Immobilized On The Terpyridine-functionalized MOFs

Metal-organic frameworks(MOFs) are a kind of inorganic-organic hybrid materials assembled with metal ions and organic ligands. Owing to their specific pore valumes and tunability, MOFs have been widely applied in the gas separation and storage, catalysis, drug release, and fluorescent probe. On the other hand, post-synthesis modification(PSM) has been investigated as a very important method to introduce useful chelators into MOFs for immobilizing active metal ions.In this thesis, a general strategy for incorporating π-conjugated NNN-chelators(e.g., terpyridyl moiety) into a porous MOF MIL-101(Cr) by using the “click” post-functionalization has been presented. X-ray diffraction(XRD) and N2 adsorption analyses confirmed that the materials retained the MOF structure and high specific surface area. The functionalized MOF could be used a platform for metalation to yield highly active and stable single-site heterogeneous metal catalysts. Terpyridine ligand can be coordinated with many transition metal ions(e.g., Ru, Pd, Ir, and Rh) to construct stable complexes with interesting catalytic properties. Preliminary metalation investigation demonstrated the synthetic utilization of MIL-101(Cr)-tpy for the construction of highly active single-site Ru(III) catalyst.Terpyridine ruthenium complexes are widely used as catalysts in redox reactions. On the other hand, selective oxidation of alcohols is an important transformation in the chemical industry. The as-prepared Ru Cl3/MIL-101-tpy material was investigated as catalyst for the oxidation of various alcohols with H2O2. The results showed that many substrates could be transformed to the corresponding aldehyde compounds in quantitative yields. Moreover, the catalyst was easily recoverable and reusable for at least five times without any apparent loss of catalytic efficiency.