Composite Catalyst of Rh/POP-BINAPa&PPh3@ZSM-35(10) for the Heterogeneous Tandem Hydroformylation–Acetalization of Olefins

Herein, we have developed a composite catalyst of Rh/POP-BINAPa&PPh3@ZSM-35(10) for the heterogeneous tandem hydroformylation–acetalization of olefins. The microstructure, surface properties, and thermal stability were characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption/desorption, and thermogravimetric analysis (TGA). A series of olefins and alcohols worked well in the process, affording the corresponding acetal products with excellent turnover number (TON) values (TON up to 10,000) and high regioselectivities (l/b = 30.2–87.9). In the 5-cycle experiment of the catalyst, no significant decrease in the yield and l/b value of the acetal products was observed. The experimental results indicated that the structure of Rh/POP-BINAPa&PPh3 in the composite catalyst was responsible for the hydroformylation process of olefins, which determined the formation of aldehydes. Subsequently, the acetalization of aldehydes with alcohol was catalyzed by ZSM-35(10) and rhodium species. In this study, the composite catalyst combines the advantages of phosphorus-containing porous polymers and molecular sieves and realizes the efficient heterogeneous tandem hydroformylation–acetalization of olefins, providing a new direction for the development of novel multifunctional composite catalytic materials.