Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers
Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers
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DOI：
10.1002/chem.201603140
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发表时间：
2017-01-05
影响因子：
4.3
通讯作者：
Weigand, Wolfgang
中科院分区：
文献类型：
--
作者：
Goy, Roman;Bertini, Luca;Weigand, Wolfgang
它成功地表明，在牺牲的电子供体，如三甲胺（TEA）和抗坏血酸盐的存在下，光催化质子还原为二氢，可以驱动紧凑的敏化剂-催化剂二联体，即，二硫羟酸桥[FeFe]氢化酶模型拴系到有机敏化剂，如芴和硅芴（1a-4a）。敏化剂-催化剂二元体1a-4a显示出显著的和有前途的催化活性，以及在UV光照射下进行的氢化期间增强的稳定性。在非水性和水性介质中进行了水化。后者的实验是通过溶解的胶束内形成的十二烷基硫酸钠（SDS）或十六烷基三甲基溴化铵（CTAB）的光催化剂。在本研究中，在优化条件下实现了539（7 h）的周转数，这对应于77 h（-1）的异常高的周转频率。理论研究以及发射衰减实验进行理解所观察到的现象与光催化H-2产生的机制。
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 (1a-4a). The sensitizer-catalyst dyads 1a-4a 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(-1). Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H-2 generation.