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The synthesis of phosphine‐based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine‐based COFs (termed P‐COFs) with well‐defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P‐COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine‐based COF family, but also demonstrates their application in immobilizing homogeneous metal‐based (e.g., Rh‐phosphine) catalysts for application in heterogeneous catalysis., A turn up for turnover: Two triphenylphosphine‐based COFs (P‐COFs) that stack in an eclipsed AA manner and have high crystallinity, high specific surface areas and good thermal stability have been synthesized. The application of these P‐COFs in phosphorus coordination catalysis was demonstrated by the hydroformylation of olefins over supported Rh/P‐COFs catalysts, which showed high turnover frequencies and excellent recycling.

A carbonylcobalt catalyst, immobilized by poly(4-vinylpyridine) (P4VP) through N→Co coordination bonds, has been prepared by solvothermal method. It has been revealed that the pyridine fragments in the polymer catalyst act not only as promoters to improve the catalytic performance of the carbonylcobalt catalyst for alkoxycarbonylation of ethylene oxide to methyl 3-hydroxypropanoate but also as stabilizers to enhance the reusability of the polymer catalyst. Furthermore, the polymer catalyst could be easily separated by filtration and reused with only a slight loss of catalytic efficiency.

The Fischer-Tropsch (FT) synthesis reaction was conducted using bimodal catalyst in a slurry phase reactor. The bimodal catalyst was prepared from a bimodal support which was tailor-made by introducing SiO2 sol directly into the large pores of a SiO2 gel pellet The bimodal catalyst exhibited significantly higher activity in the slurry-phase Fischer-Tropsch synthesis than in other unimodal catalysts. The support with a large surface area allowed a highly dispersed cobalt particle, and its large pore size improved the diffusion of reactants and products. The diffusion of reactants inside the catalyst pores was simulated, and the effects of pore structure and pore size on catalytic performances were consistent with the simulation results. © 2005 American Institute of Chemical Engineers AIChE J, 2005