Polymer-supported catalysts, example catalytic material

The potential for the use of catalysis in support of sustainability is enormous [102, 103]. New heterogeneous and homogeneous catalysts for improved reaction selectivity, and catalyst activity and stabihty, are needed, for example, new catalytic materials with new carbon modifications for nanotubes, new polymers. 

The same hyperbranched polyglycerol modified with hydrophobic palmitoyl groups was used for a noncovalent encapsulation of hydrophilic platinum Pincer [77]. In a double Michael addition of ethyl cyanoacetate with methyl vinyl ketone, these polymer supports indicated high conversion (81 to 59%) at room temperature in dichloromethane as a solvent. The activity was stiU lower compared with the noncomplexed Pt catalyst. Product catalyst separation was performed by dialysis allowing the recovery of 97% of catalytic material. This is therefore an illustrative example for the possible apphcation of such a polymer/catalyst system in continuous membrane reactors. 

Covalent bonding refers to the materials made in which the transition metal is bonded directly to the resin through an organometallic bond. Two different approaches can be used to covalently attach metal complexes to polymer supports (i) synthesis of appropriate functional monomers and their (co)polymerization to form catalytically active polymers (Scheme 11.1) or (ii) attachment of metal complexes to preformed functional polymer supports by chemical reactions. Following these approaches, both soluble and cross-linked chiral polymeric metal complexes can be prepared. An example of an organometallic tin catalyst suitable for transesterification was reported by workers at Rohm and Haas Company [3]. 

As we have commented earlier, there are some reports in where polymers are used to act as interface between the metal NPs and the G support increasing the adherence of the metal NPs to Gs. In one of these examples polypropylene imine dendrimer has been used to increase the stability of Pd-Co alloy NPs on r-GO (Scheme 3.42). This dendrimer modified r-GO catalyst is able to promote the Sonogashira coupling of alkynes and aryl halides using K COj at 25 °C. Importantly metal leaching was not observed and as a reflection of the catalyst stability, the material could be reused six times with the catalytic activity decreasing only from 99 to 93 % after the sixth cycles. 

In a differing approach to the development of insoluble, supported catalytic materials, the use of soluble polymer supports offers a possible method to facilitate the separation, subsequent recovery, and reuse of catalyst complexes. It is important to note that this often requires relatively large quantities of a non-solvent for the precipitation and recovery of the catalytic material. This is an obvious limitation, as the excess waste generates an environmental concern however, other techniques can be employed to facilitate the recovery. Examples of this include liquid/liquid phase separations or the selective precipitation of the product or catalyst from the reaction media through the use of different stimuli, such as temperature or pH. 

Bulk addition of nanoparticles refers to the use of nanoparticles as additives during the membrane synthesis process by phase inversion (Kim and Van der Braggen 2010). Nanoparticles are dispersed in the polymer solution, which is then cast on a support layer and contacted with a nonsolvent, in the case of diffusion- or nonsolvent-induced phase separation (DIPS or NIPS). In the eventual membrane, the nanoparticles are present in the inner structure of the membrane, and not exclusively on the membrane surface. Therefore, the functionalities of the nanoparticles that were used can only be partly exploited. For example, catalytic activities would not be efficient, as the nanoparticles that should act as catalyst are shielded by the polymer material. This is a concern particularly for photocatalytic materials such as Ti02, which are often employed for mixed matrix membranes. 

The new mesoporous materials have extremely high surface-to-volume ratios. An example of these materials is MCM41, which was invented by DuPont. A simple structure that can be manufactured in the laboratory is illustrated in Eigure 15.14. The structure initially contained a periodic array of polymer spheres. When close packed, these spheres leave 26% of the volume empty. We can then infiltrate a liquid into these pores, burn out the spheres, and convert the liquid to a polycrystalline ceramic. Another synthesized porous ceramic is the cordierite honeycomb structure used to support the Pt catalyst in automobile catalytic converters. In this case the cylindrical pores are introduced mechanically in the extrusion process. 

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