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

[Image: see text] Ruthenium-containing tetraphenylporphyrin (Ru-TPP) molecule was prepared, and the structural elucidation was confirmed using (1)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 (1)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, (13)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(2)) 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.