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TEMPO 和 N-羟基琥珀酰亚胺促进的 TiO 光催化协同作用用于蓝光驱动的伯胺选择性有氧氧化。

Cooperative TiO photocatalysis with TEMPO and N-hydroxysuccinimide for blue light-driven selective aerobic oxidation of amines.

机构信息

Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.

Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.

出版信息

Chemosphere. 2021 Jan;262:127873. doi: 10.1016/j.chemosphere.2020.127873. Epub 2020 Aug 9.

Abstract

TiO has been the focus of attention in semiconductor photocatalysis for several decades because it can potentially settle the grand energy and environmental issues with earth-abundant elements of Ti and O. However, because of its wide band gap, TiO can only collect UV light, hindering its practical applications under the illumination of sunlight. In view of this, an interesting phenomenon of light-driven adsorption of amines onto TiO to form a visible light-absorbing complex was adapted to assemble smart photocatalysis. The endurance of this complex was eminently refurbished by blue light-driven continuous adsorption of amines. This in turn promoted a vital selective chemical transformation, blue light-driven selective oxidation of amines into imines with atmospheric dioxygen (O). More importantly, the inclusion of TEMPO and N-hydroxysuccinimide (NHS) into the smart photocatalytic system could cooperatively expedite the blue light-driven selective aerobic oxidation of amines into imines through dual independent reaction channels, resembling that of enzymatic catalysis. This work underscores the importance of manoeuvring multiple reaction channels by cooperative photocatalysis during selective chemical transformations.

摘要

几十年来,TiO 一直是半导体光催化领域的研究焦点,因为它可以利用地球上丰富的 Ti 和 O 元素来解决重大的能源和环境问题。然而,由于其宽带隙,TiO 只能吸收紫外光,这限制了其在太阳光照射下的实际应用。有鉴于此,人们利用 TiO 光驱动吸附胺形成可见光吸收配合物的有趣现象来组装智能光催化系统。通过蓝光驱动胺的连续吸附,显著地恢复了这种配合物的耐久性。这反过来又促进了一个重要的选择性化学转化,即蓝光驱动空气中氧气(O)选择性氧化胺成亚胺。更重要的是,将 TEMPO 和 N-羟基琥珀酰亚胺(NHS)纳入智能光催化体系中,可以通过两个独立的反应通道协同加速胺的蓝光驱动选择性有氧氧化成亚胺,类似于酶催化。这项工作强调了在选择性化学转化过程中通过协同光催化来操纵多个反应通道的重要性。

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