Photoinduced Generation of a Durable Thermal Proton Reduction Catalyst with in Situ Conversion of Mn(bpy)(CO)3Br to Mn(bpy)2Br2
Photoinduced Generation of a Durable Thermal Proton Reduction Catalyst with in Situ Conversion of Mn(bpy)(CO)3Br to Mn(bpy)2Br2
复制标题
通过 Mn(bpy)(CO)3Br 原位转化为 Mn(bpy)2Br2 光诱导生成耐用热质子还原催化剂
DOI：
10.1021/acs.inorgchem.0c00480
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发表时间：
2020
影响因子：
4.6
通讯作者：
Delcamp, Jared H.
中科院分区：
文献类型：
--
作者：
Shirley, Hunter;Parkin, Sean;Delcamp, Jared H.
质子转化为氢是可再生燃料发电系统设计中的关键反应。人们非常希望能够快速促进这种还原反应的坚固、富含地球的金属基催化剂。Mn(Bpy)(CO)3Br光解质子还原反应生成活性催化剂，直接观察到的产氢速率为1 300 000次/小时，该反应的驱动力很低。通过使用FcMe10作为电子源，质子源(三氟酸、4-氰基苯胺或对甲苯磺酸)，MeCN/H2O作为溶剂，在室温下进行热反应，直到电子源完全耗尽。在10 000 000转化率范围内，没有观察到明显的催化活性损失。有趣的是，在酸存在下，Mn(Bpy)(CO)3Br3光解生成了一种可分离和表征的具有催化活性的络合物(Mn(Bpy)2Br2)。
The conversion of protons to H2is a critical reaction for the design of renewable fuel generating systems. Robust, earth-abundant, metal-based catalysts that can rapidly facilitate this reduction reaction are highly desirable. Mn(bpy)(CO)3Br generates an active catalyst for the proton reduction reaction upon photolysis at a high, directly observed H2production rate of 1 300 000 turnovers per hour, with a low driving force for this reaction. Through the use of FcMe10as an electron source, a proton source (triflic acid, 4-cyanoanilinium, or tosylic acid), and MeCN/H2O as solvent, the thermal reaction at room temperature was found to proceed until complete consumption of the electron source. No apparent loss in catalytic activity was observed to the probed limit of 10 000 000 turnovers of H2. Interestingly, a catalytically competent complex (Mn(bpy)2Br2), which could be isolated and characterized, formed upon photolysis of Mn(bpy)(CO)3Br in the presence of acid.