Catalytic systems mimicking the [FeFe]-hydrogenase active site for visible-light-driven hydrogen production

A global hydrogen economy could ensure environmentally sustainable, safe and cost-efficient renewable energy for the 21st century. Solar hydrogen production through artificial photosynthesis is a key strategy, and the activity of natural hydrogenase metalloenzymes an inspiration for the design of synthetic catalyst systems. [FeFe]-hydrogenase enzymes, present in anaerobic bacteria and green algae, are the most efficient class of biological catalysts for hydrogen evolution. The enzymes operate in an aqueous environment, utilizing electrons that ultimately stem from photosynthesis as the only energy source. Functional synthetic models of the [FeFe]-hydrogenase enzyme active site have garnered intense interest as potential catalysts for the reduction of protons to molecular hydrogen. Herein, we take an extensive journey through the field of biomimetic hydrogenase chemistry for lightdriven hydrogen production. We open with a brief presentation of the structure and redox mechanism of the natural enzyme. Synthetic methodologies, structural characteristics, and hydrogen generation metrics relevant to the synthetic diiron catalysts ([2Fe2S]) are discussed. We first examine multicomponent photocatalysis systems with the [2Fe2S] cluster, followed by photosensitizer-[2Fe2S] dyads and molecular triads. Finally, strategies for the incorporation of [2Fe2S] complexes into supramolecular assemblies, semiconductor supports, and hybrid heterogeneous platforms are laid out. We analyze the individual properties, scope, and limitations of the components present in the photocatalytic reactions. This review illuminates the most useful aspects to rationally design a wide variety of biomimetic catalysts inspired by the diiron subsite of [FeFe]-hydrogenases, and establishes design features shared by the most stable and efficient hydrogen producing photosystems. (C) 2021 The Author(s). Published by Elsevier B.V.