Department of Chemistry and Biochemistry, The University of Arizona, 1306 E. University Blvd., Tucson, AZ, 85721, USA.
Program for Chemical Convergence of Energy & Environment, School of Chemical & Biological Engineering, Seoul National University, Seoul, Korea.
Angew Chem Int Ed Engl. 2019 Jun 3;58(23):7537-7550. doi: 10.1002/anie.201813776. Epub 2019 Mar 12.
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 production.
本文综述了新型聚合物负载[2Fe-2S]催化剂体系在电催化和光催化析氢反应中的发展。[FeFe]氢化酶是已知的最适合用于产氢的天然金属酶，多年来已经合成了这些金属酶活性位点（H 簇）的小分子、[2Fe-2S]模拟物。这些小分子[2Fe-2S]配合物的产氢能力尚未达到酶的水平。最近，现代聚合物化学被用于在[2Fe-2S]簇周围构建一个外部配位球，以提供位阻隔离、水溶性和提高的催化活性。在这篇综述中，调查了各种高分子基元和这些聚合物负载的[2Fe-2S]材料的催化性能。最近的催化剂是将单个[2Fe-2S]配合物纳入其中，称为单中心[2Fe-2S]金属聚合物，其表现出优异的 H 生产活性。
