Synthesis of a palladium acetylide-based tubular microporous polymer monolith via a self-template approach: a potential precursor of supported palladium nanoparticles for heterogeneous catalysis.

A monolithic, palladium acetylide-based conjugated microporous polymer, Pd-CMP, was synthesized from a palladium dichloride and a trialkyne. The polymerization proceeded in two different ways, the dehydrohalogenation reaction between the alkyne and the palladium halide and the homocoupling reaction of the alkyne. Pd-CMP had a rigid hollow tubular structure. The in situ formed crystalline triethylammonium chloride (TEACl) rod played a critical role in the formation of the tubular morphology as a template. Through the attachment of the polymer particles to the surface of the rod and their reactions with soluble alkynes, a core-shell structure with a TEACl core and a polymer shell formed. The TEACl core was removed by washing with methanol to yield a hollow polymer tube. Pd-CMP showed a hierarchical pore structure and reversible compressibility. Supported Pd nanoparticles were prepared by one-step thermolysis of Pd-CMP as a heterogeneous catalyst. The average diameters of NPs in the products thermolyzed at 300 (Pd-CMP 300 ) and 500 °C (Pd-CMP 500 ) were 2.6 and 4.1 nm, respectively. Pd-CMP 300 was used in the heterogeneous catalysis of the 4-nitrophenol reduction reaction and Suzuki-Miyaura coupling between iodobenzene and phenylboronic acid. The reaction yields were higher than 95%. The catalyst could be used for a flow reaction and easily recycled without significant activity loss.