Tailor-made porosities of fluorene-based porous organic frameworks for the pre-designable fabrication of palladium nanoparticles with size, location and distribution control.

Porous organic frameworks (POFs) are a promising new class of support for metal nanoparticles (NPs), with the size, location and distribution of metal NPs are closely related to the porous nature of the POFs. In this contribution, three fluorene-based POFs containing coordination-inert hydrogen, propyl and benzyl substituents at the 9-position of the fluorene units (POF-1, POF-2 and POF-3) were synthesized through a simple click reaction. The substituents exerted important influences on the surface area, pore volume and pore size of the POFs. Palladium NPs with a pre-designable size, location and distribution were synthesized through a substituent-controlled strategy. When POF-1 was employed as a support, ultrafine palladium NPs in the interior pores were generated, while the introduction of propyl at the 9-position of fluorene in POF-2 gave rise to dual-distributed palladium NPs in the interior pores and on the external surface. The use of the bulkier benzyl substituent resulted in the formation of palladium NPs on the external surface of POF-3. The hydrogenation of olefins has demonstrated that palladium NPs on the external surface possessed higher catalytic activity, while palladium NPs in the interior pores exhibited higher stability and recyclability. In addition, after Pd/POF-1, Pd/POF-2 and Pd/POF-3 were stored in air over half a year, palladium NPs in the interior pores showed a negligible change in comparison with fresh samples, while an obvious agglomeration was observed for palladium NPs on the external surface.