PNNL

Abstract

The presence of a (sub)nano-metric environment has been demonstrated to enhance the rate of homogeneous acid catalyzed reactions. Conventionally, such catalysts are constructed by directly embedding a catalytic active acid site into the structure of a porous material linking the acid properties with the properties of the embedding solid. In this work, a holoenzyme mimicking approach was used, in which a self-assembled hexameric resorcinarene capsule (1.4 nm3 cavity) acts like an apoenzyme that transforms into a catalytic active site by hosting hydrated HCl as cofactor. This capsule binds the hydronium ion together with cyclohexanol and catalyzes the dehydration to cyclohexene with enhanced rates that are two orders of magnitude higher than those in the unconstrained environment.