Single atom dispersed Rh-biphephos&PPh3@porous organic copolymers: highly efficient catalysts for continuous fixed-bed hydroformylation of propene

A vinyl functionalized biphephos ligand with high steric hindrance was copolymerized with tris(4-vinphenyl)phosphane and other ligands to afford efficient porous organic copolymers (POPs) through the solvothermal synthesis technique. By employing the copolymer self-supported heterogeneous Rh/CPOL-bp&P catalysts, the hydroformylation of propene to linear-butaldehyde can be performed efficiently in a continuous fixed-bed reactor with high regioselectivity (l/b > 24), activity (TOF > 1200 h−1) and stability (over 1000 h) under mild conditions (70 °C, 0.5 MPa), which represents a substantial improvement in the efficiency of this important industrial process. EXAFS and HAADF-STEM showed that the Rh was a single atom dispersion, which explained well the high efficiency of the Rh/CPOL-bp&P catalysts. Compared with liquid–liquid biphasic (LLB) and ionic liquid (IL) systems, this highly efficient solvent free system has the advantages of simple operability, and almost no waste emission, which meets the demands of green industrial processing.