Porous aromatic frameworks with high Pd nanoparticles loading as efficient catalysts for the Suzuki coupling reaction

The development of efficient and recyclable heterogeneous Pd catalysts is an area of continuing attention due to their critical applications in organic synthesis and pharmaceutical production. In this study, two novel heterogeneous catalysts Pd@PAF-182 and Pd@PAF-183 were prepared by the immobilization/NaBH₄ reduction of PdCl₄^2- on hydrophilic cationic porous aromatic frameworks (PAF-182 and PAF-183), which were synthesized via a Yamamoto-type Ullmann coupling reaction from the corresponding aryl quaternary phosphonium salt monomer. Characterization by powder X-ray diffraction (PXRD), solid-state Cross-Polarization Magic-Angle-Spinning Nuclear Magnetic Resonance (CP/MAS NMR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) established the structures of the as-prepared catalysts. Inductively coupled plasma atomic emission spectrometry (ICP-AES) detection showed that the loading of Pd nanoparticles (Pd NPs) were 29.4 wt% for Pd@PAF-182 and 37.5 wt% for Pd@PAF-183, much higher than those of similar porous materials. Evaluation of the catalytic activity of the Pd@PAFs using Suzuki coupling as the model reaction demonstrated that as little as 0.12 mol% of Pd NPs could catalyze the Suzuki coupling with high efficiency, achieving yields up to 99% at 80 °C in 8 h. Recycling experiments also suggested that Pd@PAF-182 and Pd@PAF-183 maintained high catalytic activity with negligible leaching of Pd NPs after five cycles.