Maloul Salam, van den Borg Matthias, Müller Carolin, Zedler Linda, Mengele Alexander K, Gaissmaier Daniel, Jacob Timo, Rau Sven, Dietzek-Ivanšić Benjamin, Streb Carsten
Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081, Ulm, Germany.
Institute of Electrochemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany.
Chemistry. 2021 Dec 6;27(68):16846-16852. doi: 10.1002/chem.202103817. Epub 2021 Nov 11.
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-site 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.
多功能超分子体系是光驱动太阳能转换领域的核心研究课题。在此，我们报道了一种基于多金属氧酸盐（POM）的超分子二元体系，其中两个铂配合物析氢催化剂共价锚定在一个安德森型多氧钼酸盐阴离子上。该体系与铱光敏剂之间的超分子静电耦合实现了可见光驱动的析氢反应。理论与实验相结合证明了POM的多功能性，它既作为光敏剂/催化剂结合位点，又促进光诱导电荷转移和催化周转。对铂催化剂位点的化学修饰导致析氢反应活性增强。机理研究揭示了各个组分的作用，并提供了对控制稳定性和反应性的相互作用的分子层面理解。该体系可为能量转换和存储中的多功能多金属氧酸盐提供设计蓝本。
