Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation

Three porous organic polymers (POPs) containing H, COOMe, and COO^? groups at 2,6‐bis(1,2,3‐triazol‐4‐yl)pyridyl (BTP) units (i.e., POP‐1, POP‐2, and POP‐3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP‐1, whereas uniform‐ and dual‐distributed palladium NPs are located on the external surface of POP‐2 and POP‐3, respectively. The presence of carboxylate groups not only endows POP‐3 an outstanding dispersibility in H₂O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials.