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Multifunctional Polyoxometalate Platforms for Supramolecular Light-Driven Hydrogen Evolution** |
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| Authors: | Salam Maloul Matthias van den Borg Dr Carolin Müller Dr Linda Zedler Alexander K Mengele Daniel Gaissmaier Prof Dr Timo Jacob Prof Dr Sven Rau Prof Dr Benjamin Dietzek-Ivanšić Prof Dr Carsten Streb |
| Institution: | 1. Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany;2. Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081 Ulm, Germany;3. Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany
Leibniz Institute of Photonic Technologies (IPHT), Albert-Einstein-Straße 9, 07745 Jena, Germany;4. Leibniz Institute of Photonic Technologies (IPHT), Albert-Einstein-Straße 9, 07745 Jena, Germany;5. Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081 Ulm, Germany Helmholtz-Institute Ulm (HIU) Electrochemical Energy Storage, Helmholtzstr. 11, 89081 Ulm, Germany Karlsruhe Institute of Technology (KIT), P.O. Box 3640, 76021 Karlsruhe Karlsruhe, Germany;6. Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany |
| Abstract: | Multifunctional supramolecular systems are a central research topic in light-driven solar energy conversion. Here, we report a polyoxometalate (POM)-based supramolecular dyad, where two platinum-complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light-driven hydrogen evolution. Combined theory and experiment demonstrate the multifunctionality of the POM, which acts as photosensitizer/catalyst-binding-site1] and facilitates light-induced charge-transfer and catalytic turnover. Chemical modification of the Pt-catalyst site leads to increased hydrogen evolution reactivity. Mechanistic studies shed light on the role of the individual components and provide a molecular understanding of the interactions which govern stability and reactivity. The system could serve as a blueprint for multifunctional polyoxometalates in energy conversion and storage. |
| Keywords: | hydrogen evolution organic-inorganic hybrid polyoxometalate self-assembly supramolecular |