PNNL

Abstract

Herein, we show howthe spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis.T he underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species,analogous to outer-sphere residue cooperativity within the active sites of enzymes.This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers,enabling the desired reaction environment in close proximity to the active sites, therebyimpacting the reaction outcomes.Specifically,inthe representative dehydration of fructose to produce 5-hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1-methyl-2-pyrrolidinone and ionic liquid.