A Nanocrystal Catalyst Incorporating a Surface Bound Transition Metal to Induce Photocatalytic Sequential Electron Transfer Events
A Nanocrystal Catalyst Incorporating a Surface Bound Transition Metal to Induce Photocatalytic Sequential Electron Transfer Events
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DOI：
10.1021/jacs.1c00503
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发表时间：
2021-07-21
影响因子：
15
通讯作者：
Yan, Yong
中科院分区：
文献类型：
--
作者：
Martin, Jovan San;Zeng, Xianghua;Yan, Yong
异质光催化不太常见，但可以提供独特的途径来诱导新型化学转化，也可以用于能量转换，即光子中的能量可以在化学键中捕获。在这里，我们开发了一种新型异质光催化系统，该系统采用卤化铅钙钛矿纳米晶体（NC）捕获光子并将光生空穴引导至表面结合的过渡金属Cu位点，从而产生N-N杂环化反应。该反应从表面配位的二胺底物开始，每个反应周期需要两次后续的光氧化事件。我们建立了一个光催化途径，其中包含连续的内球电子转移事件，NC吸收的光子产生空穴，这些空穴依次汇集到铜表面位点以进行反应。该光催化剂很容易通过受控的阳离子交换反应制备，并为光驱动多相催化提供了新的机会。
Heterogeneous photocatalysis is less common but can provide unique avenues for inducing novel chemical transformations and can also be utilized for energy transductions, i.e., the energy in the photons can be captured in chemical bonds. Here, we developed a novel heterogeneous photocatalytic system that employs a lead-halide perovskite nanocrystal (NC) to capture photons and direct photogenerated holes to a surface bound transition metal Cu-site, resulting in a N-N heterocyclization reaction. The reaction starts from surface coordinated diamine substrates and requires two subsequent photo-oxidation events per reaction cycle. We establish a photocatalytic pathway that incorporates sequential inner sphere electron transfer events, photons absorbed by the NC generate holes that are sequentially funneled to the Cu-surface site to perform the reaction. The photocatalyst is readily prepared via a controlled cation-exchange reaction and provides new opportunities in photodriven heterogeneous catalysis.