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Catalytic Metallopolymers from [2Fe‐2S] Clusters: Artificial Metalloenzymes for Hydrogen Production
Author(s) -
Karayilan Metin,
Brezinski William P.,
Clary Kayla E.,
Lichtenberger Dennis L.,
Glass Richard S.,
Pyun Jeffrey
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201813776
Subject(s) - catalysis , hydrogen production , hydrogenase , chemistry , macromolecule , polymer , combinatorial chemistry , cluster (spacecraft) , active site , hydrogen , nanotechnology , materials science , organic chemistry , biochemistry , computer science , programming language
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 H 2 production.