Diiodo-BODIPY Sensitizing of the [Mo3S13]2- Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix

Daniel Costabel; Afshin Nabiyan; Avinash Chettri; Franz Jacobi; Magdalena Heiland; Julien Guthmuller; Stephan Kupfer; Maria Wächtler; Benjamin Dietzek-Ivanšić; Carsten Streb; Felix H Schacher; Kalina Peneva

doi:10.1021/acsami.2c18529

Diiodo-BODIPY Sensitizing of the [Mo₃S₁₃]^2- Cluster for Noble-Metal-Free Visible-Light-Driven Hydrogen Evolution within a Polyampholytic Matrix

ACS Appl Mater Interfaces. 2023 May 3;15(17):20833-20842. doi: 10.1021/acsami.2c18529. Epub 2023 Apr 7.

Authors

Daniel Costabel¹, Afshin Nabiyan¹, Avinash Chettri^{2

3}, Franz Jacobi¹, Magdalena Heiland⁴, Julien Guthmuller⁵, Stephan Kupfer², Maria Wächtler^{2

3}, Benjamin Dietzek-Ivanšić^{2

3

6}, Carsten Streb⁴, Felix H Schacher^{1

6}, Kalina Peneva^{1

6}

Affiliations

¹ Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Lessingstraße 8, 07743 Jena, Germany.
² Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany.
³ Leibniz Institute of Photonic Technology Jena, Albert-Einstein-Straße 9, 07745 Jena, Germany.
⁴ Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany.
⁵ Institute of Physics and Applied Computer Science, Faculty of Applied Physics and Mathematics, Gdansk University of Technology, 80233 Gdańsk, Poland.
⁶ Center for Energy and Environmental Chemistry and Jena Center of Soft Matter, Friedrich Schiller University Jena, Philosophenweg 7a, 07743 Jena, Germany.

PMID: 37026740
DOI: 10.1021/acsami.2c18529

Abstract

We report on a photocatalytic setup that utilizes the organic photosensitizer (PS) diiodo-BODIPY and the non-precious-metal-based hydrogen evolution reaction (HER) catalyst (NH₄)₂[Mo₃S₁₃] together with a polyampholytic unimolecular matrix poly(dehydroalanine)-graft-poly(ethylene glycol) (PDha-g-PEG) in aqueous media. The system shows exceptionally high performance with turnover numbers (TON > 7300) and turnover frequencies (TOF > 450 h^-1) that are typical for noble-metal-containing systems. Excited-state absorption spectra reveal the formation of a long-lived triplet state of the PS in both aqueous and organic media. The system is a blueprint for developing noble-metal-free HER in water. Component optimization, e.g., by modification of the meso substituent of the PS and the composition of the HER catalyst, is further possible.

Keywords: BODIPY; hydrogen evolution; photocatalysis; quantum chemistry; thiomolybdate.