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硫掺杂碳纳米管催化单乙醇胺溶液解吸CO2机理的理论研究

任莹莹 刘均隆 成怀刚 高阳艳

任莹莹, 刘均隆, 成怀刚, 高阳艳. 硫掺杂碳纳米管催化单乙醇胺溶液解吸CO2机理的理论研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024030
引用本文: 任莹莹, 刘均隆, 成怀刚, 高阳艳. 硫掺杂碳纳米管催化单乙醇胺溶液解吸CO2机理的理论研究[J]. 燃料化学学报(中英文). doi: 10.19906/j.cnki.JFCT.2024030
REN Yingying, LIU Junlong, CHENG Huaigang, GAO Yangyan. Theoretical study on the catalysis mechanism of sulfur-doped carbon nanotubes in CO2 desorption from monoethanolamine solution[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024030
Citation: REN Yingying, LIU Junlong, CHENG Huaigang, GAO Yangyan. Theoretical study on the catalysis mechanism of sulfur-doped carbon nanotubes in CO2 desorption from monoethanolamine solution[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024030

硫掺杂碳纳米管催化单乙醇胺溶液解吸CO2机理的理论研究

doi: 10.19906/j.cnki.JFCT.2024030
基金项目: 国家自然科学基金 (宽温域SCR催化剂上烟气中Hg0的催化氧化机理研究)资助
详细信息
    通讯作者:

    Tel: 13546390472 , E-mail: gaoyangyan@sxu.edu.cn

  • 中图分类号: O64

Theoretical study on the catalysis mechanism of sulfur-doped carbon nanotubes in CO2 desorption from monoethanolamine solution

Funds: The project was supported by National Natural Science Foundation of China ( Catalytic oxidation mechanism of Hg0 in flue gas over wide temperature range SCR catalysts).
  • 摘要: 醇胺法吸收CO2是目前最成熟的碳捕集技术,虽然吸收效率高、稳定性好,但过高的解吸能耗限制其大规模工业推广应用。催化解吸提供了降低CO2解吸能耗的可能性。本工作利用基于密度泛函理论(DFT)的量子化学模拟方法,探索了硫掺杂碳纳米管(S-CNTs)催化单乙醇胺(MEA)溶液吸收-解吸CO2反应机理。通过过渡态搜索发现,以S-CNTs为催化剂的解吸过程,决速步骤的反应能垒降低了1.15 kcal/mol。局部态密度分析表明(PDOS),产物氨基甲酸酯吸附质子化胺MEACOO-_MEAH+和吸收中间产物MEA+COO中的C、N、O原子在CNTS和S-CNTs表面吸附时PDOS差距较大。此外,与未改性CNTs相比,S-CNTS上电荷密度增加,掺杂的硫原子附近碳原子具有明显的电负性。相比于CNTs,吸收中间产物MEA+COO和吸收产物MEACOO-MEAH+均向S-CNTs转移了更多的电荷,表明更多的电荷转移有利于CO2的释放。本工作旨在通过CO2催化解吸机理的研究为催化剂的设计提供一定的理论依据。
  • 图  1  S-CNTS结构示意图

    Figure  1  Schematic diagram of S-doped CNTS structure

    yellow ball represents Satoms, gray represents Catoms.

    图  2  (a)MEA-CO2和MEA-CO2-CNTS/ S-CNTS催化反应路径的能量变化(b)对应的结构示意图

    Figure  2  (a) Energy changes in the catalytic reaction path of MEA-CO2 and MEA-CO2-CNTS / S-CNTS (b) Schematic diagram of the corresponding structure

    图  3  (a) MEA-CO2-CNTS/S-CNTS催化反应路径结构的静电势图 和(b) 电荷密度图 (c) 差分电荷密度图

    Figure  3  (a) Electrostatic potential diagram of the structure of the catalytic reaction pathway of MEA-CO2-CNTS/S-CNTS and (b) Charge density diagram (c) Differential charge density diagramR1 / R refers to the reactant monoethanolamine solution and CO2 in the catalytic desorption reaction, IM 1 refers to the intermediate zwitterion ZW in the catalytic desorption reaction, IM 2 refers to the intermediate ZW and single ethanolamine solution in the catalytic desorption reaction, P1 / P refers to the products carbamate and protonation amine, TS1 and TS2 are transition states.

    图  4  (a)CNTS/S-CNTS结构中C、S等原子的PDOS图(b)CNTS/S-CNTS_R1催化反应结构中C、N、O等原子的PDOS图

    Figure  4  PDOS plots of C, N, O and other atoms in the structure of the CNTS/S-CNTS_R1 catalytic reaction and PDOS maps of C and S and other atoms in the CNTS / S-CNTS structure(The red ball represents oxygen atoms, the gray ball represents C atoms, the yellow ball represents S atoms,the white ball represents H atoms, and the blue ball represents N atoms)

    图  5  CNTS/S-CNTS_IM1催化反应结构中C、N、O等原子的PDOS图

    Figure  5  XX

    图  6  CNTS/S-CNTS_P1催化反应结构中C、N、O等原子的PDOS图

    Figure  6  XX

    图  7  MEA-CO2-S-CNTS催化反应路径结构中C、S、O原子的PDOS图和 精确分子模型系空间充满式模型(Corey-Pauling-koltun,CPk)模式

    Figure  7  The PDOS diagram of C, S and O atoms in structure of MEA-CO2-S-CNTS catalytic reaction pathway and the exact molecular model of S-CNTS adsorption structure are space-filled model (Corey-Pauling-koltun, CPk) mode (Red balls represent oxygen atoms, gray balls represent carbon atoms,yellow balls represent sulfur atoms, and white balls represent hydrogen atoms)

    表  1  不同反应物/吸收产物/中间态吸附在碳纳米管/S掺杂碳纳米管上的吸附能

    Table  1  Adsorption energy of different reactants/desorption products/intermediate states adsorbed on carbon nanotubes/S-doped carbon nanotubes

    Materials MEA CO2 MEACOO MEAH+ MEA_CO2 MEA+COO MEA+COO−_MEA MEACOO−_MEAH+
    Ead(CNTs)/(kcal·mol−1) −3.728 −1.489 −57.228 −5.582 −3.528 −2.700 −3.531
    Ead(S-CNTs)/(kcal·mol−1) −2.229 −0.242 −26.322 −56.306 −2.484 −2.748 −2.748 −5.846
    注:碳纳米管吸附了吸收产物MEACOO-之后,然后经过结构优化发现MEACOO分解成了MEA和CO2
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  • 收稿日期:  2024-02-22
  • 修回日期:  2024-04-21
  • 录用日期:  2024-04-26
  • 网络出版日期:  2024-06-04

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