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

We review the development of novel polymer‐supported [2Fe‐2S] catalyst systems for electrocatalytic and photocatalytic hydrogen evolution reactions and the enhancement observed in these metallopolymer materials. [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 reached the same capacity of the enzymes for hydrogen production thus far. Recently, modern polymer chemistry has been utilized to construct a biomimetic outer coordination sphere around the [2Fe‐2S] clusters to provide site isolation, water solubility and improved catalytic activity. In this review, we discuss on the various macromolecular motifs used to incorporate catalytic [2Fe‐2S] clusters. We survey both the conjugation methods and catalytic properties of these polymer‐supported [2Fe‐2S] materials where we discuss metallopolymers that incorporate [2Fe‐2S] complexes using either supramolecular, or covalent attachment methods. Catalysts that encapsulate a single [2Fe‐2S] complex, termed, single‐site [2Fe‐2S] metallopolymers were observed to exhibit superior activity for H2 production.

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