Ruthenium-Based Macromolecules as Potential Catalystsin Homogeneous and Heterogeneous Phases for the Utilization of CarbonDioxide

摘要

Ruthenium-containing tetraphenylporphyrin (Ru-TPP) molecule was prepared, and the structural elucidation was confirmed using ¹H nuclear magnetic resonance (NMR), CHN, and mass spectral analyses. The incorporation of ruthenium ion into the cavities of the macromolecule was confirmed from the disappearance of the ¹H NMR signal, characteristic of the N–H bond (−2.72 ppm in TPP). The CHN and mass spectral analyses of the ligand and metallomacromolecules are consistent with the theoretically calculated values. The homogeneous Ru-TPP macromolecule is grafted on the surface of aminosilane-, diaminosilane-, and iodosilane-functionalized SBA-15 molecular sieves. The successful grafting of Ru-TPP on functionalized mesoporous molecular sieve materials was evident from low-angle powder X-ray diffraction, ¹³C magic angle spinning NMR, and scanning electron microscopy–energy-dispersive X-ray analyses. The resultant homogeneous and heterogenized Ru-TPP catalysts were used for the utilization of carbon dioxide (CO2) under moderate reaction conditions. The homogeneous Ru-TPP catalyst showed first-order kinetics with respect to epoxide with the exclusive formation of cyclic carbonate (about98%) and an activation energy of 16.07 kg/mol, which is much lowerthan some of the reported catalysts. Ru-TPP grafted on aminosilane-and iodosilane-functionalized materials showed better catalytic activity(above 90% conversion and 83–96% cyclic carbonate selectivity)and reusability for the chosen reaction.