A new and efficient hydrophilicity-directed approach (HDA) is developed to encapsulate large guest molecules beyond the aperture size limitation in the nanospace of metal-organic frameworks (MOFs), as exemplified by the self-assembly of a metal-organic polyhedral (MOP) M6L4 into MIL-101. This strategy is based on the different hydrophilicities between inner and outer surfaces of the preformed MOF that may direct the self-assembly of the MOP in the MOF pores by using a two-solvent system. Importantly, as the MOP guest molecule is larger than the MOF aperture size, aggregation and leaching are effectively prevented, endowing the encapsulated MOP with significantly enhanced reactivity and stability in the catalytic transformations as compared to the pristine MOP.

Core–shell Pd@Ag nanoparticles are formed within the pores of MOFs via a seed mediated growth strategy with activated hydrogen atoms as the reducing agent, leading to a family of bimetallic core–shell MOF nanomaterials with excelling catalytic performance in room temperature reactions.

A highly efficient, simple, and versatile transition-metal-free metal-organic framework catalytic system is proposed for the oxidative coupling of amines to imines. The catalytic protocol features high activities and selectivities to target products; compatibility with a variety of substrates, including aliphatic amines and secondary amines; and the possibility to efficiently and selectively promote amine cross-coupling reactions. A high stability and recyclability of the catalyst is also observed under the investigated conditions. Insights into the reaction mechanism indicate the formation of a superoxide species able to efficiently promote oxidative couplings.

A simple and versatile synthetic route is develped to modulate the growth and distribution of MOF-graphene oxide (GO) nanohybrid materials, achieving dense and ordered MOFs featuring different sizes and morphologies on GO. After pyrolysis, the resulting metal-containing/rGO nanomaterials demonstrate a superior catalytic activity in organic transformations.