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Inhibitory effect of Zn2+ on the chain-initiation process of cumene oxidation
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  • Zhicheng Chen,
  • Yuhang Li,
  • Yonghai Cao,
  • Qiao Zhang,
  • Hao Yu,
  • Feng Peng
Zhicheng Chen
Guangzhou University
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Yuhang Li
Sun Yat-Sen University
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Yonghai Cao
South China University of Technology
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Qiao Zhang
Guangzhou University
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Hao Yu
South China University of Technology
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Feng Peng
Guangzhou University
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Abstract

Carbon nanotubes (CNTs) have excellent catalytic activity in liquid phase reaction, especially in aerobic oxidation of cumene. In previous work, the conversion of cumene was 41.8% and the selectivity of cumene hydroperoxide was 71.5%, which was catalyzed by CNTs. But a small amount of impurity Zn2+ totally blocked up the aerobic oxidation of cumene that catalyzed by CNTs, which is an unexpected discovery. By analyzing the catalytic mechanism of CNTs, the inhibition effect of Zn2+ is locked on the abstraction of H atom from cumene. The inhibition of Zn2+ is confirmed in two effects by density functional theory (DFT) calculations. Firstly, due to the strongly coordination of active oxygen species (ROS) by Zn2+, the energy barrier of initial reaction increases to 1.90 eV, which is nearly 4 times higher than that of the only ROS promoted-process. Secondly, the interaction of Zn2+ and RO· or ROO· to inhibits the chain propagation reaction of free radicals. This work precisely demonstrates that the inhibition effect of Zn2+ on initial reaction of cumene. The most significant thing is that the effect of metallic heteroatoms is not negligible in organic oxidation reaction.

Peer review status:ACCEPTED

15 Apr 2021Submitted to International Journal of Quantum Chemistry
16 Apr 2021Submission Checks Completed
16 Apr 2021Assigned to Editor
04 May 2021Reviewer(s) Assigned
18 May 2021Review(s) Completed, Editorial Evaluation Pending
19 May 2021Editorial Decision: Revise Major
24 Jun 20211st Revision Received
25 Jun 2021Submission Checks Completed
25 Jun 2021Assigned to Editor
25 Jun 2021Reviewer(s) Assigned
08 Jul 2021Review(s) Completed, Editorial Evaluation Pending
09 Jul 2021Editorial Decision: Accept