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

• Published in: ACS applied materials & interfaces 2023-05, Vol.15 (17), p.20833-20842
• Main Authors: Costabel, Daniel, Nabiyan, Afshin, Chettri, Avinash, Jacobi, Franz, Heiland, Magdalena, Guthmuller, Julien, Kupfer, Stephan, Wächtler, Maria, Dietzek-Ivanšić, Benjamin, Streb, Carsten, Schacher, Felix H., Peneva, Kalina
• Format: Article
• Language: English
• Subjects: Energy, Environmental, and Catalysis Applications
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.2c18529

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.