Ruthenium-Based Macromolecules as Potential Catalysts in Homogeneous and Heterogeneous Phases for the Utilization of Carbon Dioxide.

Ruthenium-containing tetraphenylporphyrin (Ru-TPP) molecule was prepared, and the structural elucidation was confirmed using H 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 H 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, C 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 (CO) under moderate reaction conditions. The homogeneous Ru-TPP catalyst showed first-order kinetics with respect to epoxide with the exclusive formation of cyclic carbonate (about 98%) and an activation energy of 16.07 kg/mol, which is much lower than 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.