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计算研究取代基对仲胺与CO2反应动力学过程的影响

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谢宏彬, 王攀, 陈景文. 计算研究取代基对仲胺与CO2反应动力学过程的影响[J]. 环境化学, 2016, 35(2): 237-245. doi: 10.7524/j.issn.0254-6108.2016.02.2015092303
引用本文: 谢宏彬, 王攀, 陈景文. 计算研究取代基对仲胺与CO2反应动力学过程的影响[J]. 环境化学, 2016, 35(2): 237-245. doi: 10.7524/j.issn.0254-6108.2016.02.2015092303
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XIE Hongbin, WANG Pan, CHEN Jingwen. Substituent effects on kinetics process for the reaction of secondary amines with CO2:A computational study[J]. Environmental Chemistry, 2016, 35(2): 237-245. doi: 10.7524/j.issn.0254-6108.2016.02.2015092303
Citation: XIE Hongbin, WANG Pan, CHEN Jingwen. Substituent effects on kinetics process for the reaction of secondary amines with CO2:A computational study[J]. Environmental Chemistry, 2016, 35(2): 237-245. doi: 10.7524/j.issn.0254-6108.2016.02.2015092303
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计算研究取代基对仲胺与CO2反应动力学过程的影响

  • 1.

    工业生态与环境工程教育部重点实验室, 大连理工大学环境学院, 大连, 116024

  • 基金项目:

    国家自然科学基金(21207016,21325729),中央高校基本科研经费(DUT12RC(3)07),辽宁省教育厅(L2012021)及长江学者与创新团队发展计划(IRT_13R05)资助.

Substituent effects on kinetics process for the reaction of secondary amines with CO2:A computational study

  • 1.

    Key Laboratory of Industrial Ecology and Environmental Engineering(MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, China

  • Fund Project: Supported by the National Natural Science Foundation of China(21207016, 21325729), the Fundamental Research Funds for the Central Universities(DUT12RC(3)07), the Liaoning Provincial Education Department(L2012021) and Program for Changjiang Scholars and Innovative Research Team in University(No.IRT_13R05).

  • 摘要: 本文选取取代的二乙醇胺(DEA)为模型化合物,利用量子化学方法研究了5种不同电负性的取代基(-CH3、-NH2、-OH、-OCH3、-F)分别在DEA氮原子的α和β位取代对仲胺与CO2不同反应路径之间的动力学竞争的影响.研究表明,从动力学方面来看,胺与CO2反应生成氨基甲酸盐是最可行的反应通道,其次是生成碳酸氢盐,而生成氨基甲酸难以实现. 3条反应路径的动力学竞争顺序和伯胺是相同的.研究发现,反应能垒Ea除与胺的pKa值相关外,还与胺的分子结构特性相关,比如:分子内氢键的形成会影响Ea.在将来的理想胺溶液的设计过程中,要综合考虑胺的pKa值及胺的微观结构对胺与CO2反应的动力学的影响.
    Abstract: Amines have been considered as promising candidates for post-combustion CO2 capture due to their high absorption efficiency and low partial pressure requirement. It is important to investigate the effects of amine structures on their reaction kinetics, competition among different reaction pathways for rational design of amines. In this study, diethanolamine(DEA) was selected as the model compound and -CH3,-NH2,-OH,-OCH3, and -F substituents at both α-and β-carbon positions of DEA were considered. Quantum chemical methods were used to investigate substituent effects on kinetic competition of typical pathways for the reaction of DEA with CO2. The computed Ea values indicate that the formation of carbamate is the most favored, followed by that to form bicarbonate, while the formation of carbamic acid is not feasible for all the considered amines. The Ea order of kinetic competition for three pathways is the same with that of primary amines. In addition, It was found the Ea values are influenced not only by pKa of amines, but also by molecular structures of amines, e.g. intramolecular hydrogen bond. Both pKa and molecular structure of amines should be considered as important influencing factors in future amine design.
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  • 收稿日期:  2015-09-23
  • 刊出日期:  2016-02-15

计算研究取代基对仲胺与CO2反应动力学过程的影响

  • 1. 工业生态与环境工程教育部重点实验室, 大连理工大学环境学院, 大连, 116024
  • 收稿日期:  2015-09-23
基金项目:

国家自然科学基金(21207016,21325729),中央高校基本科研经费(DUT12RC(3)07),辽宁省教育厅(L2012021)及长江学者与创新团队发展计划(IRT_13R05)资助.

摘要: 本文选取取代的二乙醇胺(DEA)为模型化合物,利用量子化学方法研究了5种不同电负性的取代基(-CH3、-NH2、-OH、-OCH3、-F)分别在DEA氮原子的α和β位取代对仲胺与CO2不同反应路径之间的动力学竞争的影响.研究表明,从动力学方面来看,胺与CO2反应生成氨基甲酸盐是最可行的反应通道,其次是生成碳酸氢盐,而生成氨基甲酸难以实现. 3条反应路径的动力学竞争顺序和伯胺是相同的.研究发现,反应能垒Ea除与胺的pKa值相关外,还与胺的分子结构特性相关,比如:分子内氢键的形成会影响Ea.在将来的理想胺溶液的设计过程中,要综合考虑胺的pKa值及胺的微观结构对胺与CO2反应的动力学的影响.

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