Enhancing Singlet Oxygen Photocatalysis with Plasmonic Nanoparticles
Enhancing Singlet Oxygen Photocatalysis with Plasmonic Nanoparticles
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DOI：
10.1021/acsami.1c05892
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发表时间：
2021-07-26
影响因子：
9.5
通讯作者：
Moores, Audrey
中科院分区：
文献类型：
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作者：
Gelle, Alexandra;Price, Gareth D.;Moores, Audrey
能够引发单线态氧物质的产生的光催化剂是有机合成中密集研究努力的主题。然而，在改善其活动和优化其使用方面仍然存在挑战。在本文中，我们利用等离子体纳米颗粒的优点，通过可见光范围内的天线效应来提高这种光催化剂的活性。我们合成了二氧化硅包覆的银纳米颗粒（Ag@SiO2 NPs），其具有厚度范围为7至45 nm的二氧化硅壳。我们发现，他们担任三（联吡啶）钌（II），[Ru（bpy）（3）]（2+）的等离子体活性载体，并表现出增强的催化活性下，白色发光二极管（LED）照射香茅醇氧化，在商业生产的玫瑰氧化物香料的关键步骤。用28 nm二氧化硅层观察到等离子体介导的反应性的约3倍的最大增强，沿着光催化剂的发射强度增强4倍。使用电子能量损失谱（EELS）和边界元方法模拟，我们映射的等离子体信号的衰减周围的银核心，并提供了一个基本原理所观察到的催化增强。这项工作提供了一个有前途的性能的等离子体纳米粒子作为催化增强支持常见的均相光催化剂和成功设计这样的系统在有机转化的背景下的框架进行了系统的分析。
Photocatalysts able to trigger the production of singlet oxygen species are the topic of intense research efforts in organic synthesis. Yet, challenges still exist in improving their activity and optimizing their use. Herein, we exploited the benefits of plasmonic nanoparticles to boost the activity of such photocatalysts via an antenna effect in the visible range. We synthesized silica-coated silver nanoparticles (Ag@SiO2 NPs), with silica shells which thicknesses ranged from 7 to 45 nm. We showed that they served as plasmonically active supports for tris(bipyridine)ruthenium(II), [Ru(bpy)(3)](2+), and demonstrated an enhanced catalytic activity under white light-emitting diode (LED) irradiation for citronellol oxidation, a key step in the commercial production of rose oxide fragrance. A maximum enhancement of the plasmon-mediated reactivity of approximately 3-fold was observed with a 28 nm silica layer along with a 4-fold enhancement in the emission intensity of the photocatalyst. Using electron energy loss spectroscopy (EELS) and boundary element method simulations, we mapped the decay of the plasmonic signal around the Ag core and provided a rationale for the observed catalytic enhancement. This work provides a systematic analysis of the promising properties of plasmonic NPs used as catalysis-enhancing supports for common homogeneous photocatalysts and a framework for the successful design of such systems in the context of organic transformations.