Covalent Heme Framework as a Highly Active Heterogeneous Biomimetic Oxidation Catalyst

Although the active centers of many metalloenzymes have been well-studied, the ability for chemists to imitate the iron porphyrin heme found in these enzymes remains a challenge. Herein, we report a water/chemical-stable nanoporous covalent heme framework (CHF-1) that can be synthesized via the Yamamoto homocoupling reaction. Unlike other artificial enzymes, CHF-1 neatly arranges the heme centers to form a graphene-like two-dimensional framework bearing a high surface area (1620 m 2 /g) and high density of active sites. Biomimetic catalytic reactions show that CHF-1 catalyst is an effective heterogeneous catalyst with exceptionally high binding affinities and high catalytic efficiency approaching that of natural heme-based enzymes.