High-efficiency photo-oxidation of thioethers over C60@PCN-222 under air†,Journal of Materials Chemistry A

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High-efficiency photo-oxidation of thioethers over C60@PCN-222 under air†
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2019-09-05 , DOI: 10.1039/c9ta07965c
Deng-Yue Zheng _{1,

2,

3,

4,

5} , En-Xuan Chen _{1,

2,

3,

4,

5} , Chun-Rong Ye _{1,

2,

3,

4,

5} , Xiao-Chun Huang _{1,

2,

3,

4,

5}

Affiliation

The selective oxidation of primary thioethers to sulfoxides is an important reaction in the production of pharmaceuticals, agrochemicals, and other valuable fine chemicals. However, the achievement of high conversion and selectivity towards sulfoxide during thioether oxidation under mild conditions still remains a great challenge. In this study, we found a new method to overcome the abovementioned challenge by applying the C₆₀@PCN-222 composite as a catalyst in the photo-oxidation of thioethers. The C₆₀@PCN-222 composite was obtained by the integration of guest C₆₀ molecules and a porous porphyrin-based metal–organic framework (MOF), PCN-222; we proposed that the photogenerated electron–hole separation of PCN-222 could be significantly enhanced through the encapsulation of C₆₀ molecules with a large, highly delocalized π-conjugation, which provided a great contribution to the high conversion and selectivity of this type of reaction. Under air and low optical power (50 mW cm⁻²) conditions at room temperature, the composite exhibited excellent catalytic performance; we further explored the underlying mechanism of action of this photocatalyst by investigating the reactive oxygen species via ESR spectral analysis and adjusting the experimental conditions. It has been revealed that superoxide radicals, generated by electron transfer from a photoexcited MOF to the C₆₀ molecules, serve as the main active species for the oxidation.

中文翻译：

空气中 C ₆₀ @ PCN-222上的硫醚高效光氧化†

伯硫醚选择性氧化为亚砜是制药，农药和其他有价值的精细化学品生产中的重要反应。然而，在温和条件下在硫醚氧化过程中实现高转化率和对亚砜的选择性仍然是一个巨大的挑战。在这项研究中，我们发现了一种通过将C ₆₀ @ PCN-222复合材料用作硫醚的光氧化催化剂来克服上述挑战的新方法。C ₆₀ @ PCN-222复合材料是通过访客C ₆₀的整合获得的分子和基于卟啉的多孔金属有机框架（MOF），PCN-222；我们提出，通过将C ₆₀分子与大的高度离域的π共轭包封，可以显着增强PCN-222的光生电子-空穴分离，这对此类反应的高转化率和选择性做出了巨大贡献。在室温下在空气和低光功率（50 mW cm ^-2）条件下，该复合材料表现出优异的催化性能。我们通过研究活性氧种类，进一步探索了这种光催化剂的潜在作用机理。ESR光谱分析和调整实验条件。已经发现，由电子从光激发的MOF转移到C ₆₀分子产生的超氧自由基是氧化的主要活性物质。

更新日期：2019-10-02

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