Amine-Functionalized Microporous Organic Nanotube Frameworks Supported Pt and Pd Catalysts for Selective Oxidation of Alcohol and Heck Reactions

We report a synthesis of amine-functionalized microporous organic nanotube frameworks supported Pt or Pd catalysts (Pt or Pd@NH₂-MONFs) by a combination of hyper cross-linking tricomponent bottlebrush copolymers and subsequent gentle reduction. In this method, the intrabrush and interbrush cross-linking of polystyrene (PS) shell layer in the tricomponent bottlebrush copolymers led to the formation of micropores and large-sized nanopores (meso/macrospores) in NH₂-MONFs, respectively, while selective removal of polylactide (PLA) core layer generated mesoporous tubular structure. Interestingly, the middle functional poly(Boc-aminoethyl acrylamide) (PBAEA) component could be deprotected to produce the free amine moieties in the channel of MONFs, which will play a key role to anchor Pt or Pd nanoparticles on the support by an in situ reduction with NaBH₄. Owing to their high special surface area, robust organic framework, and hierarchically porous structure, the resultant Pt or Pd@NH₂-MONFs show high heterogeneous catalytic activity and excellent reusability in the selective oxidation of alcohol and Heck reactions, respectively.