Polymer supported metal catalysts encapsulation

Entrapment or intercalation of metal species in pores and cavities of solid supports has frequently been used for the immobilization of catalysts in inorganic materials such as zeolites, clays, charcoals, silicas, aluminas, and other solids. Though this review article focuses on the immobilization of palladium complexes on polymer supports via covalent and/or coordination bonds, recent novel approaches to polymer-supported palladium species (including palladium nanoparticles) via nonbonding immobilization, such as encapsulation and incarceration, are intriguing because of their high potential for utility. In this section, several representatives are introduced. 

Dendrimer-encapstdated catalysts are another area of active research for polymer-supported catalysts. The nanoparticles are stabilized by the dendrimers preventing precipitation and a omeration. Bimetallic nanoparticles with encapsulated metals (dendrimer-encapsulated catalyst DEC) from commercially available fourth-generation PAMAM dendrimers and palladium and platinum metal salts were prepared via reduction by Crooks and co-workers [34], following previous work in this area [35], The simultaneous incorporation of Pt and Pd reflects the concentrations in solution. The bimetallic DECs are more active than the physical mixture of single-metal DEC [35, 36] in the case of the hydrogenahon of allyl alcohol in water, with a maximum TOP of 230 h compared to TOP = 190 h obtained for monometallic palladium nanoparticles (platinum TOP = 50 h ). 

In this specific case, the colloid stabilizers are dendrimers, for instance, polyamidoamine (PAMAM), which are hyperbranched polymers that ramify from a single core and form a porous sphere [103, 104] (Scheme 17.1). Dendrimer-encapsulated nanoparticles (DENs) are synthesized by sequestering metal ions within appropriate dendrimers, and then by chemically reducing the resulting composite. They can be synthesized in various media, such as water or ethanol. The size of the nanoparticles is usually nearly monodisperse, and can be tuned by varying the metal-to-dendrimer ratio prior to reduction. Supported catalysts can then he prepared by immobilizing DENs onto a sohd support. As in the case of colloids, the last step, which consists in the removal of dendrimers hy thermal treatment, may lead to an increase in both the metal-particle size and particle-size distribution. 

---