Nano-space confinement of pre-selective catalysts for hydroformylation of 1-octene

Ph.D. (Chemistry)Rhodium-catalyzed hydroformylation is one of the most important industrial processes for the production of linear and branch aldehydes. Aldehydes serve as intermediates in the production of various fine chemicals. Rh-based homogeneous catalysts for aldehydes production have demonstrated high yields and selectivity. Catalyst separation and recovery of expensive Rh-metal from reaction mixtures is a challenge to this process. With increasing industrial demand for highly selective processes, homogeneous catalysis could well be extensively employed if catalyst recovery from products and recyclability could be accomplished more efficiently and economically. The above problems justify the investigation of immobilized (heterogenized) catalysts by both academia and industry. This would solve the separation problem by making it possible to separate the catalyst from the reaction medium with simple filtration techniques and to regenerate the catalyst for reuse. Moreover, the ease of recovery of catalyst from products and reusability can minimize the impact of the process on the environment. Immobilization of metal complexes on solid supports is an effective approach to overcome the limitations of homogeneous catalysis. Support materials such as Mobil Composite Material (MCM-41) and Santa Barbara Amorphous type material (SBA-15) are attractive candidates for immobilizing metal complexes because of their high surface area, adjustable pore sizes, large pore volumes and high surface silanol groups. In the present work, mesoporous silica supports, MCM-41 and SBA-15 were synthesized. Rhodium(I) complex species, trans-aquacarbonyl bis(triphenylphosphine) [Rh(CO)(OH2)(PPh3)2]OTf and trans-aquacarbonyl bis{tris-(m-sulfonphenyl)-phosphine} [Rh(CO)(OH2)(TPPTS)2]OTf were synthesized as catalyst precursors and anchored onto the mesoporous MCM-41 and SBA-15 framework structure via an electrostatic method to form immobilized (heterogenized) catalysts. The support and catalyst were characterized using a range of solid-state techniques. Results showed that the structural integrity of the catalyst supports was maintained after immobilization. Results also revealed a strong interaction between rhodium complex species and the inner walls of the ordered mesoporous materials, thus leading to the formation of stable heterogenized catalysts. In addition, immobilized catalysts constrained the pores, thus leading to a confinement effect, which enhanced activity and regioselectivity in the hydroformylation process. Selected immobilized catalysts were..