Activating a [FeFe] Hydrogenase Mimic for Hydrogen Evolution under Visible Light

Philipp Buday; Chizuru Kasahara; Elisabeth Hofmeister; Daniel Kowalczyk; Micheal K Farh; Saskia Riediger; Martin Schulz; Maria Wächtler; Shunsuke Furukawa; Masaichi Saito; Dirk Ziegenbalg; Stefanie Gräfe; Peter Bäuerle; Stephan Kupfer; Benjamin Dietzek-Ivanšić; Wolfgang Weigand

doi:10.1002/anie.202202079

Activating a [FeFe] Hydrogenase Mimic for Hydrogen Evolution under Visible Light

Angew Chem Int Ed Engl. 2022 May 9;61(20):e202202079. doi: 10.1002/anie.202202079. Epub 2022 Mar 23.

Authors

Philipp Buday¹, Chizuru Kasahara^{1

2}, Elisabeth Hofmeister³, Daniel Kowalczyk⁴, Micheal K Farh¹, Saskia Riediger⁵, Martin Schulz^{3

6}, Maria Wächtler^{3

6

7}, Shunsuke Furukawa², Masaichi Saito², Dirk Ziegenbalg⁴, Stefanie Gräfe^{6

7

8

9}, Peter Bäuerle⁵, Stephan Kupfer⁶, Benjamin Dietzek-Ivanšić^{3

6

7

8}, Wolfgang Weigand¹

Affiliations

¹ Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldtstraße 8, 07743, Jena, Germany.
² Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama City, Saitama, 338-8570, Japan.
³ Department Functional Interfaces, Leibniz Institute of Photonic Technology Jena (Leibniz-IPHT), Albert-Einstein-Straße 9, 07745, Jena, Germany.
⁴ Institute of Chemical Engineering, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
⁵ Institute of Organic Chemistry II and Advanced Materials, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
⁶ Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743, Jena, Germany.
⁷ Abbe Center of Photonics (ACP), Friedrich Schiller University Jena, Albert-Einstein-Straße 6, 07745, Jena, Germany.
⁸ Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena, Philosophenweg 8, 07743, Jena, Germany.
⁹ Fraunhofer Institute for Applied Optics and Precision Engineering, Albert-Einstein-Straße 7, 07745, Jena, Germany.

Abstract

Inspired by the active center of the natural [FeFe] hydrogenases, we designed a compact and precious metal-free photosensitizer-catalyst dyad (PS-CAT) for photocatalytic hydrogen evolution under visible light irradiation. PS-CAT represents a prototype dyad comprising π-conjugated oligothiophenes as light absorbers. PS-CAT and its interaction with the sacrificial donor 1,3-dimethyl-2-phenylbenzimidazoline were studied by steady-state and time-resolved spectroscopy coupled with electrochemical techniques and visible light-driven photocatalytic investigations. Operando EPR spectroscopy revealed the formation of an active [Fe^I Fe⁰ ] species-in accordance with theoretical calculations-presumably driving photocatalysis effectively (TON≈210).

Keywords: H2 Production; Oligothiophene; Operando EPR Spectroscopy; Photocatalysis; [FeFe] Hydrogenase Mimics.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Hydrogen / chemistry
Hydrogenase* / metabolism
Iron-Sulfur Proteins* / chemistry
Light

Substances

Iron-Sulfur Proteins
Hydrogen
Hydrogenase