Nanoclustered palladium(0) supported on a gel-type poly-acrylonitrile-N,N-dimethylacrylamide-ethylenedimethacrylate resin: Nanostructural aspects and catalytic behaviour

Gel-type resin poly-acrylonitrile (30 mol%)–N,N-dimethylacrylamide (66 mol%)–ethylenedimethacrylate (4 mol%) (ADE) is obtained in very high yield with -rays-sustained polymerisation in mass. Water-swollen ADE microparticles react readily with [PdCl4 2−] in water to give a macromolecular complex likely to be . The material undergoes facile reduction to a Pd0/ADE nanocomposite, in which a surprisingly non-homogeneous distribution of Pd0 nanoclusters suggests a remarkable inhomogeneity in the distribution of the –CN groups through the polymer framework. This circumstance is attributed to a marked occurrence of a block-type polymerisation of the acrylonitrile leading to spheroidal domains that are particularly rich in –CN functionalities. Pd0/ADE appears to be an active, re50 usable, mechanically and chemically stable catalyst in the model hydrogenation reaction of cyclohexene in methanol under moderate conditions, carried out in batch reactors.