Metal nanoparticles, once supported by a suitable scaffolding material, can be used as highly efficient heterogeneous catalysts for numerous organic reactions. The challenge, though, is to mitigate the continuous loss of metals from the supporting materials as reactions proceed, so that the catalysts can be recycled multiple times. Herein, we combine the excellent chelating property of chitosan (CS) and remarkable stability of montmorillonite (MMT) into a composite material to support metal catalysts such as palladium (Pd). The in situ reduction of Pd2+ into Pd0 in the interstices of MMT/CS composites effectively encages the Pd0 nanoparticles in the porous matrices, while still allowing for reactant and product molecules of relatively small sizes to diffuse in and out the matrices. The prepared Pd0@MMT/CS catalysts are highly active for the Heck reactions of aromatic halides and alkenes, and can be recycled 30 times without significant loss of activities. Positron annihilation lifetime analysis and other structural characterization methods are implemented to elucidate the unique compartmentalization of metal catalysts in the composite matrices. As both CS and MMT are economical and abundant materials in nature, this approach may facilitate a versatile platform for developing highly recyclable, heterogeneous catalysts containing metal nanoparticles.
Keywords: chitosan; heterogeneous catalysis; montmorillonite; palladium; positron annihilation.