The incorporation of catalysts into polymeric materials often relies on catalyst incorporation post-polymerization, which can lead to imperfect loading, low dispersity of the desired catalytic polymer, and impurities in the polymer structure. By covalently attaching electronically isolated units suitable for ring-opening metathesis polymerization onto stable catalyst centers, it is possible to create addressable polymer structures from active catalysts. Not only do these catalytic monomer units retain activity in the polymer structure, the resultant polymers are living and may be co-polymerized with monomers that tune the catalytic reaction. Since both catalyst density and activity may be altered, and the resultant polymer structures can incorporate solubilizing, co-catalytic, or secondary catalyst units, this method can be used to develop optimized macromolecular catalyst structures for a variety of reactions. Initial studies with a Re bipyridine-based electrocatalyst for the reduction of CO2show that the exclusion of solvent by the polymer itself can increase catalyst turnover frequency. Since this is a proton-dependent reaction, the inclusion of proton sources also contributes to lowering the operating potential. By altering the solubility of the polymer or choice of solvent, these structures may be investigated as both homogeneous and heterogeneous catalysts.

Catalytic polymer structures with addressable co-catalyst composition and active site densities

248th National Meeting (2014)

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