Mechanistic study of photocatalytic CO(2) reduction using a Ru(ii)-Re(i) supramolecular photocatalyst.
Mechanistic study of photocatalytic CO(2) reduction using a Ru(ii)-Re(i) supramolecular photocatalyst.
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DOI：
10.1039/d1sc02213j
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发表时间：
2021-07-21
期刊：
影响因子：
8.4
通讯作者：
Ishitani O
中科院分区：
文献类型：
--
作者：
Kamogawa K;Shimoda Y;Miyata K;Onda K;Yamazaki Y;Tamaki Y;Ishitani O
包含[Ru(二亚胺)3]2+光敏剂和fac-[Re(二亚胺)(CO)3{OC(O)OC2H4NR2}]催化剂单元的超分子光催化剂可用于以高选择性、耐久性和效率将CO2还原为CO。在三乙醇胺存在下，Re催化剂单元有效地吸收CO2形成碳酸酯络合物，然后使用此类超分子光催化剂可以实现低浓度CO2（例如10％CO2）的直接光催化还原。在这项工作中，利用时间分辨可见光和红外光谱以及电化学方法，研究了具有碳酸酯配体的超分子光催化剂RuC2Re光催化还原CO2的机理。利用时间分辨光谱测量，详细阐明了单电子还原物质RuC2(Re)−（光催化反应中重要的中间体）的光化学形成过程的动力学，并阐明了其电子结构。这些研究还表明，RuC2(Re)− 在反应溶液中可稳定稳定 10 毫秒。除了稳态辐射产生的 RuC2(Re)− 的温度和动力学分析之外，在不同扫描速率下测量的循环伏安图表明，RuC2(Re)− 的后续反应在 298 K 下以观察到的约 1.8 s−1 的一级速率常数进行，并且是单分子反应，与 CO2 和 RuC2(Re)− 的浓度无关。详细研究了光催化 CO2 还原的重要中间体（具有碳酸酯配体的 Ru(ii)-Re(i) 超分子光催化剂的单电子还原物质）的形成过程和反应活性。
Supramolecular photocatalysts comprising [Ru(diimine)3]2+ photosensitiser and fac-[Re(diimine)(CO)3{OC(O)OC2H4NR2}] catalyst units can be used to reduce CO2 to CO with high selectivity, durability and efficiency. In the presence of triethanolamine, the Re catalyst unit efficiently takes up CO2 to form a carbonate ester complex, and then direct photocatalytic reduction of a low concentration of CO2, e.g., 10% CO2, can be achieved using this type of supramolecular photocatalyst. In this work, the mechanism of the photocatalytic reduction of CO2 was investigated applying such a supramolecular photocatalyst, RuC2Re with a carbonate ester ligand, using time-resolved visible and infrared spectroscopies and electrochemical methods. Using time-resolved spectroscopic measurements, the kinetics of the photochemical formation processes of the one-electron-reduced species RuC2(Re)−, which is an essential intermediate in the photocatalytic reaction, were clarified in detail and its electronic structure was elucidated. These studies also showed that RuC2(Re)− is stable for 10 ms in the reaction solution. Cyclic voltammograms measured at various scan rates besides temperature and kinetic analyses of RuC2(Re)− produced by steady-state irradiation indicated that the subsequent reaction of RuC2(Re)− proceeds with an observed first-order rate constant of approximately 1.8 s−1 at 298 K and is a unimolecular reaction, independent of the concentrations of both CO2 and RuC2(Re)−. Formation processes and reactivity of an important intermediate of photocatalytic CO2 reduction, one-electron reduced species of a Ru(ii)–Re(i) supramolecular photocatalyst with a carbonate ester ligand, were investigated in detail.
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影响因子：
1.8
作者：
HAWECKER, J;LEHN, JM;ZIESSEL, R
通讯作者：
ZIESSEL, R
DOI：
10.1039/c39830000536
发表时间：
1983-01-01
影响因子：
--
作者：
HAWECKER, J;LEHN, JM;ZIESSEL, R
通讯作者：
ZIESSEL, R
影响因子：
3.6
作者：
Nakagawa, Tatsuo;Okamoto, Kido;Katoh, Ryuzi
通讯作者：
Katoh, Ryuzi
影响因子：
15
作者：
Agarwal, Jay;Fujita, Etsuko;Muckerman, James T.
通讯作者：
Muckerman, James T.
影响因子：
4.6
作者：
Gholamkhass, B;Mametsuka, H;Ishitani, O
通讯作者：
Ishitani, O