Theoretical Investigation on Denitrification Mechanism of Piperidine: Effects of Methylation Versus Protonation on C–N Bond Activation

  • Houyu Zhu
  • Guixia Li
  • Yongqing Gong
  • Xin Li
  • Xuefei Ding
  • Xiaoqing LuEmail author
  • Lianming Zhao
  • Yuhua Chi
  • Wenyue GuoEmail author


The denitrification mechanisms of piperidine, 2-methylpiperidine (2-MP), and 2,6-dimethylpiperidine (2,6-DMP) on MoP(001) were studied using self-consistent periodic density functional theory (DFT). These molecules located at Mo top site via the N atom and the molecular planes parallel with MoP surface. The energy barrier of the C–N bond cleavage of piperidinium (protonated piperidine) was much lower than that of the direct C–N bond cleavage of piperidine, indicating of a promoting effect of the protonation on the C–N bond cleavage, and the same trend was also found for 2-MP and 2,6-DMP. Our calculations suggested that the α-position methylation would not facilitate the hydrogenolysis pathway (protonation and subsequent C–N bond cleavage) of piperidine, in accordance with the experimental results. Both the protonation and α-position methylation could promote the C–N bond cleavage of piperidine on MoP(001), and the positive effect of protonation on C–N bond activation was more significant than that of the methylation.

Graphic Abstract


Piperidine Denitrification C–N bond cleavage MoP DFT 



This work was supported by Natural Science Foundation of China (21776315), Natural Science Foundation of Shandong Province (ZR2017MB053), PetroChina Innovation Foundation (2016D-5007-0401, 2017D-5007-0402), and the Fundamental Research Funds for the Central Universities (17CX02031A, 19CX05001A).

Compliance with Ethical Standards

Conflict of interest

All the authors declare that they have no conflict of interest.


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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Houyu Zhu
    • 1
  • Guixia Li
    • 1
    • 2
  • Yongqing Gong
    • 1
  • Xin Li
    • 1
  • Xuefei Ding
    • 1
  • Xiaoqing Lu
    • 1
    Email author
  • Lianming Zhao
    • 1
  • Yuhua Chi
    • 1
  • Wenyue Guo
    • 1
    Email author
  1. 1.School of Materials Science and EngineeringChina University of Petroleum (East China)QingdaoChina
  2. 2.Science and Information Science CollegeQingdao Agriculture UniversityQingdaoChina

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