Facile One-Step Metal–Organic Framework Surface Polymerization Method

A simple one-step approach that only uses commercially available small-molecule reagents was developed for the construction of metal–organic framework (MOF)@polymer core–shell composite particles. Here, the MOF particles were incorporated into a typical reversible addition–fragmentation chain-transfer (RAFT) polymerization solution containing a solvent, a chain-transfer agent, an initiator, and a monomer mixture with at least one hydrogen-bond-donating monomer such as 2-hydroxyethyl methacrylate or acrylic acid. The elongation of polymer chains during polymerization gradually increases MOF/polymer interfacial interaction and eventually results in the adsorption of a random copolymer onto the MOF surface through hydrogen-bond cross-linking and MOF/polymer interfacial interaction. The continuous growth of the polymer leads to a uniform polymer coating on the MOF. Benefiting from the tacky polymer surface, these well-defined MOF@polymer composite particles can be further assembled into highly ordered monolayer composite thin films either alone or with an additional polymer matrix through the Langmuir–Blodgett technique.