Catalytic Metallopolymers from [2Fe‐2S] Clusters: Artificial Metalloenzymes for Hydrogen Production

Reviewed herein is the development of novel polymer‐supported [2Fe‐2S] catalyst systems for electrocatalytic and photocatalytic hydrogen evolution reactions. [FeFe] hydrogenases are the best known naturally occurring metalloenzymes for hydrogen generation, and small‐molecule, [2Fe‐2S]‐containing mimetics of the active site (H‐cluster) of these metalloenzymes have been synthesized for years. These small [2Fe‐2S] complexes have not yet reached the same capacity as that of enzymes for hydrogen production. Recently, modern polymer chemistry has been utilized to construct an outer coordination sphere around the [2Fe‐2S] clusters to provide site isolation, water solubility, and improved catalytic activity. In this review, the various macromolecular motifs and the catalytic properties of these polymer‐supported [2Fe‐2S] materials are surveyed. The most recent catalysts that incorporate a single [2Fe‐2S] complex, termed single‐site [2Fe‐2S] metallopolymers, exhibit superior activity for H2 production. Besser als das Original: In jüngsten Studien wurde moderne Polymerchemie genutzt, um makromolekulare Trägerstrukturen in der Umgebung der biomimetischen [2Fe‐2S]‐Zentren von [FeFe]‐Hydrogenasen zu konstruieren, welche die Katalyse der Wasserstoffproduktion verbessern. Dieser Kurzaufsatz fasst die bisherigen Ansätze und katalytischen Eigenschaften dieser Systeme zusammen. Die neuesten Konstrukte arbeiten in neutralem Wasser und in Luft, wobei die H2‐Produktionsraten die der Hydrogenasen übertreffen.