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醇类有氧氧化过程中前所未有的CuO-CD纳米超结构的同时形成及其在炔丙基胺化反应中的催化应用:一种同时催化和金属废物增值(SCMWV)方法。

Unprecedented Concomitant Formation of CuO-CD Nano-Superstructures During the Aerobic Oxidation of Alcohols and Their Catalytic Use in the Propargylamination Reaction: A Simultaneous Catalysis and Metal Waste Valorization (SCMWV) Method.

作者信息

Patil Rani N, Vijay Kumar A

机构信息

Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai, Maharashtra 400019, India.

出版信息

ACS Omega. 2017 Oct 5;2(10):6405-6414. doi: 10.1021/acsomega.7b00898. eCollection 2017 Oct 31.

Abstract

Copper-cyclodextrins (CDs)-catalyzed aerobic oxidation of alcohols under aqueous conditions and a concomitant formation of CuO-cyclodextrin nano-superstructures (CuO-CD nps) during the reaction are reported. The use of affordable copper and cyclodextrin combination for aerobic oxidation precluding organic solvents makes it a benign methodology. Intriguingly, a diverse array of CuO-CD nps with unique morphologies was obtained by varying copper salts, cyclodextrins, and bases. The nano-superstructures were characterized by different techniques, such as X-ray diffraction, X-ray photoelectron spectroscopy, differential scanning calorimetry-thermogravimetric analysis, scanning electron microscopy, time of flight secondary-ion mass spectrometry, and transmission electron microscopy to confer their authenticity. Interestingly, the nano-superstructures showed promising catalytic efficiency for a one-pot three-component propargylamination reaction. The used particles were found to be recoverable and recyclable for propargylamination for up to three cycles, with no loss of catalytic activity. Moreover, the concomitant formation of CuO-CD nanostructures and their self-segregation during an aerobic oxidation reaction under homogenous conditions is a first-of-its-kind method depicting simultaneous catalysis and metal waste valorization (SCMWV). Overall, this new approach of reaping the benefits of homogenous metal catalysis and simultaneously sequestrating the metal into a high-value product might pave the way to develop many such SCMWV protocols in future.

摘要

报道了铜 - 环糊精(CDs)在水相条件下催化醇的有氧氧化,以及反应过程中伴随形成的CuO - 环糊精纳米超结构(CuO - CD纳米粒子)。使用价格低廉的铜和环糊精组合进行有氧氧化,无需有机溶剂,使其成为一种良性方法。有趣的是,通过改变铜盐、环糊精和碱,可以获得一系列形态独特的CuO - CD纳米粒子。通过X射线衍射、X射线光电子能谱、差示扫描量热 - 热重分析、扫描电子显微镜、飞行时间二次离子质谱和透射电子显微镜等不同技术对纳米超结构进行了表征,以证实其真实性。有趣的是,这些纳米超结构对一锅三组分炔丙基胺化反应显示出有前景的催化效率。发现所用颗粒可回收并循环用于炔丙基胺化反应多达三个循环,且催化活性无损失。此外,在均相条件下的有氧氧化反应过程中伴随形成CuO - CD纳米结构及其自分离,是一种前所未有的方法,展示了同时催化和金属废物增值(SCMWV)。总体而言,这种利用均相金属催化的益处并同时将金属螯合到高价值产物中的新方法,可能为未来开发许多此类SCMWV方案铺平道路。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6755/6645271/3a3825c03971/ao-2017-00898r_0008.jpg

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