The Redox Coupling Effect in a Photocatalytic Ru-II-Pd-II Cage with TTF Guest as Electron Relay Mediator for Visible-Light Hydrogen-Evolving Promotion
The Redox Coupling Effect in a Photocatalytic Ru-II-Pd-II Cage with TTF Guest as Electron Relay Mediator for Visible-Light Hydrogen-Evolving Promotion
复制标题
以 TTF 客体为电子中继介体的光催化 Ru-II-Pd-II 笼中的氧化还原耦合效应促进可见光析氢
DOI：
10.1002/anie.201913303
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Su Cheng-Yong
中科院分区：
文献类型：
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作者：
Wu Kai;Li Kang;Chen Sha;Hou Ya-Jun;Lu Yu-Lin;Wang Jing-Si;Wei Mei-Juan;Pan Mei;Su Cheng-Yong
通过光诱导电子转移（PET）过程的氧化还原客体调制，证明了氧化还原RuII - pdii金属-有机笼（MOC - 16）的纳米笼耦合效应可以有效地光化学产氢。通过与MOC - 16的光氧化还原循环耦合，TTF客体作为电子中继介质，在长时间尺度上提高了主客体体系的整体电子传递效率，从而显著促进了可见光驱动的H2evolution。相比之下，在没有主客体相互作用的体溶液中存在较大的TTF -衍生物会干扰MOC - 16的PET过程，导致H2evolution效率低下。这种相互作用为理解氧化还原活性纳米笼和客体之间的相互作用提供了一个例子，用于优化氧化还原事件和光催化活性在受限的化学纳米环境中。
A nanocage coupling effect from a redox RuII‐PdIImetal–organic cage (MOC‐16) is demonstrated for efficient photochemical H2production by virtue of redox–guest modulation of the photo‐induced electron transfer (PET) process. Through coupling with photoredox cycle of MOC‐16, tetrathiafulvalene (TTF) guests act as electron relay mediator to improve the overall electron transfer efficiency in the host–guest system in a long‐time scale, leading to significant promotion of visible‐light driven H2evolution. By contrast, the presence of larger TTF‐derivatives in bulk solution without host–guest interactions results in interference with PET process of MOC‐16, leading to inefficient H2evolution. Such interaction provides an example to understand the interplay between the redox‐active nanocage and guest for optimization of redox events and photocatalytic activities in a confined chemical nanoenvironment.