用于可见光驱动制氢的双核光催化剂的活性修复

Active repair of a dinuclear photocatalyst for visible-light-driven hydrogen production.

作者信息

Pfeffer Michael G, Müller Carolin, Kastl Evelyn T E, Mengele Alexander K, Bagemihl Benedikt, Fauth Sven S, Habermehl Johannes, Petermann Lydia, Wächtler Maria, Schulz Martin, Chartrand Daniel, Laverdière François, Seeber Phillip, Kupfer Stephan, Gräfe Stefanie, Hanan Garry S, Vos Johannes G, Dietzek-Ivanšić Benjamin, Rau Sven

机构信息

Institute of Inorganic Chemistry I (Materials and Catalysis), Ulm University, Ulm, Germany.

Institute of Physical Chemistry, Friedrich Schiller University Jena, Jena, Germany.

出版信息

Nat Chem. 2022 May;14(5):500-506. doi: 10.1038/s41557-021-00860-6. Epub 2022 Feb 7.

Abstract

The molecular apparatus behind biological photosynthesis retains its long-term functionality through enzymatic repair. However, bioinspired molecular devices designed for artificial photosynthesis, consisting of a photocentre, a bridging ligand and a catalytic centre, can become unstable and break down when their individual modules are structurally compromised, halting their overall functionality and operation. Here we report the active repair of such an artificial photosynthetic molecular device, leading to complete recovery of catalytic activity. We have identified the hydrogenation of the bridging ligand, which inhibits the light-driven electron transfer between the photocentre and catalytic centre, as the deactivation mechanism. As a means of repair, we used the light-driven generation of singlet oxygen, catalysed by the photocentre, to enable the oxidative dehydrogenation of the bridging unit, which leads to the restoration of photocatalytic hydrogen formation.

摘要

生物光合作用背后的分子装置通过酶修复保持其长期功能。然而,为人工光合作用设计的受生物启发的分子装置,由光中心、桥连配体和催化中心组成,当其各个模块的结构受到破坏时,可能会变得不稳定并分解,从而停止其整体功能和运作。在此,我们报告了这种人工光合分子装置的活性修复,导致催化活性完全恢复。我们已确定桥连配体的氢化作用是失活机制,它会抑制光中心与催化中心之间的光驱动电子转移。作为一种修复手段,我们利用光中心催化产生单线态氧,使桥连单元进行氧化脱氢,从而恢复光催化产氢。

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