Activating a [FeFe] Hydrogenase Mimic for Hydrogen Evolution under Visible Light. Issue 20 (23rd March 2022)

• Record Type: Journal Article
• Authors: Buday, Philipp; Kasahara, Chizuru; Hofmeister, Elisabeth; Kowalczyk, Daniel; Farh, Micheal K.; Riediger, Saskia; Schulz, Martin; Wächtler, Maria; Furukawa, Shunsuke; Saito, Masaichi; Ziegenbalg, Dirk; Gräfe, Stefanie; Bäuerle, Peter; Kupfer, Stephan; Dietzek‐Ivanšić, Benjamin; Weigand, Wolfgang
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 20(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-23
• Subjects: H2 Production -- Oligothiophene -- Operando EPR Spectroscopy -- Photocatalysis -- [FeFe] Hydrogenase Mimics; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202202079
• Languages: English
• ISSNs: 1433-7851

Abstract

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 Fe 0 ] species—in accordance with theoretical calculations—presumably driving photocatalysis effectively (TON≈210). Abstract : A precious metal‐free photocatalyst PS‐CAT consisting of a [FeFe] hydrogenase mimic was utilized in the scope of hydrogen generation under visible light. The dyad comprising a π‐conjugated oligothiophene as light absorber shows a remarkably high photocatalytic activity. In accordance with theory, operando EPR spectroscopy using BIH as sacrificial donor reveals the generation of an active [Fe I Fe 0 ] species during the irradiation experiment.