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Amphiphilic Carbon Quantum Dots as a Bridge to a Pseudohomogeneous Catalyst for Selective Oxidative Cracking of Alkenes to Aldehydes: A Nonmetallic Oxidation System

  • Leila Hadian-Dehkordi
    Leila Hadian-Dehkordi
    Nano Drug Delivery Research Center, Health Technology Institute, Kermanshah University of Medical Sciences, Kermanshah 67145-1673, Iran
  • Aram Rezaei*
    Aram Rezaei
    Nano Drug Delivery Research Center, Health Technology Institute, Kermanshah University of Medical Sciences, Kermanshah 67145-1673, Iran
    *Email: [email protected], [email protected]
    More by Aram Rezaei
  • Ali Ramazani
    Ali Ramazani
    Department of Chemistry, University of Zanjan, Zanjan 45371-38791, Iran
    More by Ali Ramazani
  • Mehdi Jaymand
    Mehdi Jaymand
    Nano Drug Delivery Research Center, Health Technology Institute, Kermanshah University of Medical Sciences, Kermanshah 67145-1673, Iran
  • Hadi Samadian
    Hadi Samadian
    Nano Drug Delivery Research Center, Health Technology Institute, Kermanshah University of Medical Sciences, Kermanshah 67145-1673, Iran
  • Lingxia Zheng
    Lingxia Zheng
    Department of Applied Chemistry, Zhejiang University of Technology, Hangzhou 310032, China
    State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310032, China
  • Xiaolei Deng
    Xiaolei Deng
    Department of Applied Chemistry, Zhejiang University of Technology, Hangzhou 310032, China
    State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310032, China
    More by Xiaolei Deng
  • , and 
  • Huajun Zheng
    Huajun Zheng
    Department of Applied Chemistry, Zhejiang University of Technology, Hangzhou 310032, China
    State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310032, China
    More by Huajun Zheng
Cite this: ACS Appl. Mater. Interfaces 2020, 12, 28, 31360–31371
Publication Date (Web):June 29, 2020
https://doi.org/10.1021/acsami.0c05025
Copyright © 2020 American Chemical Society
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Abstract

The oxidative cleavage of alkenes to the corresponding aldehydes using new amphiphilic carbon quantum dots (A-CQDs) as a pseudohomogeneous carbocatalyst is achieved for the first time through green and sustainable chemical processes. In this work, we successfully design a recyclable pseudohomogeneous catalyst based on A-CQDs, which is decorated with 1-aminopropyl-3-methyl-imidazolium chloride and stearic acid. The functionalization is conducted to introduce a hydrophilic/hydrophobic functionality on the surface of the catalyst to achieve high catalyst availability in polar and nonpolar media with the green goal of eliminating organic (co)solvents and additives. This amphiphilic carbocatalyst provides high mass transferability to the biphasic system, which is beneficial to promoting the oxidative cracking of a variety of olefins into corresponding aldehydes with a substrate/A-CQD ratio of 150. Around 87% of the substrates are converted to the related aldehydes using the carbocatalyst in the presence of H2O2, in pure water, without using a phase-transfer catalyst or any additives and organic solvents, which is comparable with the current metal-based cleavage systems. Surprisingly, A-CQDs exhibit high catalytic activity for the scission of electron-deficient C═C bond of coumarin derivatives, accompanied by the cleavage of C–O bonds to produce the corresponding salicylaldehyde derivatives without overoxidation to acid. As a brief conclusion, A-CQDs exhibit high conversion efficiency without significant loss of activity even after six catalytic cycles. The conversion of alkenes into aldehydes is fast and high-throughput without overoxidation to acids and is accompanied by excellent solubility and stability in various solvents. Moreover, the product and the catalyst are recoverable from the reaction medium by simple extraction. So, this pseudohomogeneous carbocatalyst promises new horizons in imminent “catalytic age”. All in all, this paper provides a significant and novel advancement in carbocatalyst chemistry.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c05025.

  • Overall XPS spectrum of A-CQDs; TGA and DTG for A-CQDs; FT-IR, 1H NMR, and 13C NMR spectra of the mixture of 4-chlorocinnamic acid reaction; and 1H NMR and 13C NMR spectra of the mixture of coumarin-3-carboxylic acid reaction (PDF)

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This article is cited by 10 publications.

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  2. Aram Rezaei, Leila Hadian-Dehkordi, Hadi Samadian, Mehdi Jaymand, Homa Targhan, Ali Ramazani, Hadi Adibi, Xiaolei Deng, Lingxia Zheng, Huajun Zheng. Pseudohomogeneous metallic catalyst based on tungstate-decorated amphiphilic carbon quantum dots for selective oxidative scission of alkenes to aldehyde. Scientific Reports 2021, 11 (1) https://doi.org/10.1038/s41598-021-83863-0
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