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 mim...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-06, Vol.58 (23), p.7537-7550
Main Authors: Karayilan, Metin, Brezinski, William P., Clary, Kayla E., Lichtenberger, Dennis L., Glass, Richard S., Pyun, Jeffrey
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Catalytic activity
Clusters
energy conversion
enzymes
Hydrogen
Hydrogen evolution reactions
Hydrogen production
Macromolecules
metallopolymers
Organic chemistry
Polymer chemistry
Polymers
water splitting
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Summary: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. The going rate: Recently, modern polymer chemistry has been utilized to construct macromolecular supports around the butterfly [2Fe‐2S] active‐site mimetics of [FeFe] hydrogenases to improve the catalysis of hydrogen production. This Minireview summarizes the approaches and catalytic properties reported to date for these systems. The most recent constructs operate in neutral water and in air with the rates of H2 production exceeding those of the hydrogenases.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201813776