脯氨酸离子液体催化CO<sub>2</sub>合成碳酸丙烯酯机理的密度泛函理论研究

绪连彩; 张智强; 彭琼阳; 毛明; 邵晨; 蒋玲; 王国庆

doi:10.3969/j.issn.2096-1553.2016.1.014

January 2016

Article Contents

XU Lian-cai, ZHANG Zhi-qiang, PENG Qiong-yang, et al. Density functional theory studies on the mechanism of the synthesis propylene carbonate by CO2 catalyzed proline ionic liquids[J]. Journal of Light Industry, 2016, 31(1): 89-95. doi: 10.3969/j.issn.2096-1553.2016.1.014

Citation: XU Lian-cai, ZHANG Zhi-qiang, PENG Qiong-yang, et al. Density functional theory studies on the mechanism of the synthesis propylene carbonate by CO2 catalyzed proline ionic liquids[J]. Journal of Light Industry, 2016, 31(1): 89-95. doi: 10.3969/j.issn.2096-1553.2016.1.014 shu

Density functional theory studies on the mechanism of the synthesis propylene carbonate by CO₂ catalyzed proline ionic liquids

College of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China

Received Date: 2015-11-20

Abstract

The possible reaction paths of synthesis of propylene carbonate catalyzed by proline ionic liquid were studied by density functional theory (DFT).The geometries of reactants, transition states and products were optimized at M06/6-31+G(d) theoretical level.All stationary point and transition states were verified according to the number of imaginary frequency through harmonic vibrational analysis, transition states were also confirmed by intrinsic reaction coordinate analysis.Single point energy for each species was recalculated at M06/6-311++G(2d,p) theoretical level.The results indicated that 2,4-pentanedione was activated by proline anion through a proton transfer reaction to yield 2,4-pentanedione anion which contained a carbon anion.The synthesis of propylene carbonate was catalyzed by the 2,4-pentanedione anion.Alternatively, the 2,4-pentanedione anion was able to be carboxylated by CO₂.The carboxylated 2,4-pentanedione anion showed a higher catalytic activity, however, the carboxylation reaction was a thermodynamic unfavorable process.
- density functional theory,
- proline ionic liquids,
- CO₂ catalytic,
- propylene carbonate
References
1. [1]
  张锁江,刘晓敏,姚晓倩,等.离子液体的前沿、进展及应用[J].中国科学:B辑,2009, 39(10):1134.
2. [5] ZHANG Z Q, XU L C, FENG W K. Intermolecular proton transfer in cyclic carbonate synthesis from epoxide and carbon dioxide catalyzed by azaphosphatranes: a DFT mechanistic study[J].RSC advances,2015,5(16):12382.
3. [8] JANG D Y,JANG H G,KIM G R.Synthesis of chiral propylene carbonate via asymmetric ring opening of racemic propylene oxide by carbon dioxide on immobilized cobalt salen catalyst[J].Catal today, 2012, 185(1):306.
4. [9] BARTOK M. Advances in immobilized organocatalysts for heterogeneous asymmetric direct aldol reactions[J].Catalysis reviews: science & engineering, 2015, 57(2):192.
5. [5]
  [10] SONG H B,YU Y H,CHEN X W,et al.2-Pyrrolidinecarboxylic acid ionic liquid catalyzed Knoevenagel condensation[J].Chinese journal of catalysis,2012,33(4):666.
6. [6]
  [11] GRIMME S, ANTONY J, EHRLICH S, et al.A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu[J].J Chem Phys, 2010, 132(15):154104.
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