Goy Roman, Bertini Luca, Rudolph Tobias, Lin Shu, Schulz Martin, Zampella Giuseppe, Dietzek Benjamin, Schacher Felix H, De Gioia Luca, Sakai Ken, Weigand Wolfgang
Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, Humboldtstraße 8, 07743, Jena, Germany.
Department of Biotechnology and Biosciences, University of Milano-Bicocca, 20126, Milan, Italy.
Chemistry. 2017 Jan 5;23(2):334-345. doi: 10.1002/chem.201603140. Epub 2016 Dec 2.
It is successfully shown that photocatalytic proton reduction to dihydrogen in the presence of a sacrificial electron donor, such as trimethylamine (TEA) and ascorbate, can be driven by compact sensitizer-catalyst dyads, that is, dithiolate-bridged [FeFe] hydrogenase models tethered to organic sensitizers, such as fluorenes and silafluorenes (1 a-4 a). The sensitizer-catalyst dyads 1 a-4 a show remarkable and promising catalytic activities as well as enhanced stabilities during photocatalysis performed under UV-light irradiation. The photocatalysis was carried out both in non-aqueous and aqueous media. The latter experiments were performed by solubilizing the photocatalysts within micelles formed by either sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB). In this study a turnover number of 539 (7 h) is achieved under optimized conditions, which corresponds to an exceptionally high turnover frequency of 77 h . Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H generation.
结果成功表明，在牺牲电子供体（如三甲胺（TEA）和抗坏血酸盐）存在的情况下，光催化质子还原为氢气可由紧密的敏化剂 - 催化剂二元体系驱动，即与有机敏化剂（如芴和硅芴（1 a - 4 a））相连的二硫醇盐桥连[FeFe]氢化酶模型。敏化剂 - 催化剂二元体系1 a - 4 a在紫外光照射下进行的光催化过程中表现出显著且有前景的催化活性以及增强的稳定性。光催化在非水和水介质中均进行。后者的实验是通过将光催化剂溶解在由十二烷基硫酸钠（SDS）或十六烷基三甲基溴化铵（CTAB）形成的胶束中来进行的。在本研究中，在优化条件下实现了539（7小时）的周转数，这对应于77 h的异常高的周转频率。进行了理论研究以及发射衰减实验，以了解观察到的现象以及光催化产氢的机制。
