钒金属-有机骨架上胺和硫化物的可见光驱动光催化选择性氧化,Sustainable Energy & Fuels

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钒金属-有机骨架上胺和硫化物的可见光驱动光催化选择性氧化
Sustainable Energy & Fuels ( IF 5.0 ) Pub Date : 2022-10-13 , DOI: 10.1039/d2se01152b
Ke Guo _{1,

2} , Guang'an Jie ₁ , Jiahui Liu ₁ , Yanghe Fu _{1,

3} , Rui Ma _{1,

3} , Xinqing Lu _{1,

3} , Fumin Zhang _{1,

3} , Weidong Zhu _{1,

3} , Maohong Fan ₄

Affiliation

有机合成中的光催化选择性氧化已成为一种环境友好且能源可持续的方法来生产有价值的化学品，但它仍然是一个巨大的挑战。在这项研究中，由基于三苯基的有机连接体构成的钒 ( IV ) 金属-有机骨架，名为 BIT-66，首先被用作在分子氧或叔叔存在下选择性氧化胺和硫化物的光催化剂。-丁基过氧化氢（TBHP）。BIT-66具有高效的可见光吸收和光致电荷产生特性，在可见光下具有高选择性的氧化反应生成有价值的亚胺或亚砜的优异光催化性能，以及良好的可重复使用性。通过进一步研究活性氧光催化反应的大量猝灭实验和电子顺磁共振俘获测量。研究发现，由激发的 BIT-66 的光生电子转移产生的超氧自由基可能是胺氧化偶联中的主要活性物质，而羟基和过氧自由基共同在硫化物的氧化中起关键作用。 TBHP 作为氧化剂。这项研究证明了光活性 MOF 在有机转化以生产有价值的化学品方面的巨大潜力。

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Visible-light-driven photocatalytic selective oxidation of amines and sulfides over a vanadium metal–organic framework

Photocatalytic selective oxidation in organic synthesis has been emerging as an environmentally friendly and energy sustainable approach to produce valuable chemicals, yet it remains a great challenge. In this study, a vanadium(IV) metal–organic framework constructed from triphenyl-based organic linkers, named BIT-66, was first employed as a photocatalyst for the selective oxidation of amines and sulfides in the presence of molecular oxygen or tert-butyl hydroperoxide (TBHP). BIT-66 possesses efficient visible-light absorption and photoinduced charge generation properties, and exhibits an excellent photocatalytic performance for oxidation reactions to produce valuable imines or sulfoxides with a high selectivity under visible light, as well as good reusability. The reactive oxygen species were further investigated via lots of quenching experiments and electron paramagnetic resonance trapping measurements for photocatalytic reactions. It is found that the superoxide radicals, resulting from the photogenerated electron transfer of the excited BIT-66, could be the main active species in the oxidative coupling of amines, while both hydroxyl and peroxyl radicals together play crucial roles in the oxygenation of sulfides using TBHP as the oxidant. This study demonstrates the great potential of photoactive MOFs for organic transformations to produce valuable chemicals.

更新日期：2022-10-13

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