基于分子模拟的新型双阳离子质子型离子液体捕集CO2研究

doi:10.11949/0438-1157.20240791

摘要/Abstract

摘要：

有机超强碱质子离子液体作为一种绿色溶剂，在CO₂捕集领域展现出独特优势。选择由1，8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）和N-叔丁基二乙醇胺（NtBuDEA）反应生成的有机超强碱双阳离子质子型离子液体[DBUH]₂[NtBuDEA]为吸收剂，通过密度泛函理论和分子动力学模拟分析其与CO₂之间的微观结构、作用机理及吸收过程。研究发现，阴离子[NtBuDEA]^2-的烷基氧负离子在CO₂吸收过程中发挥关键作用，与CO₂发生化学键合作用，生成烷基碳酸盐[NtBuDEACOO]^2-。CO₂分子从气相扩散到吸收剂表面并在气/液界面处聚集，其吸收量在达到最大值后围绕平均值波动。温度和压力是影响CO₂吸收的关键因素，降低吸收温度和提高CO₂分压有利于CO₂的捕集。水的存在虽降低了吸收剂与CO₂的相互作用能，却提高了CO₂的传输性能。

关键词: 碳捕集, 离子液体, 密度泛函理论, 分子动力学, 微观机理

Abstract:

As a green solvent, organic superbase proton-type ionic liquids show unique advantages in the field of CO₂ capture. In this work, we investigated the organic super base dual-cation protic ionic liquid [DBUH]₂[NtBuDEA], synthesized via the reaction between 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and N-tert-butyl-diethanolamine (NtBuDEA). The microstructure, action mechanism and absorption process between the [DBUH]₂[NtBuDEA] and CO₂were analyzed by density functional theory (DFT) and molecular dynamics (MD) simulation. The results demonstrated that the anion [NtBuDEA]^2-is critical for CO₂ absorption, engaging in chemical bonding with CO₂ to form the alkyl carbonate [NtBuDEACOO]^2-. Additionally, CO₂ molecules diffuse rapidly from the gas phase to the surface of absorbent and accumulate at the gas/absorbent interface. The amount of absorbed CO₂ fluctuates around the average value after reaching maximum absorption. Temperature and pressure are key factors influencing CO₂ uptake and it is favorable for CO₂ capture through decreasing the reaction temperature and increasing the CO₂ partial pressure. Although the existence of water reduces the interaction energy between the absorbent and CO₂, it enhances CO₂ transfer performance, particularly under high pressure conditions, where the CO₂absorption capacity per molar ionic liquid in water-containing ionic liquids surpasses that in pure ionic liquids.

Key words: CO₂ capture, ionic liquids, density functional theory, molecular dynamics, microcosmic mechanism

中图分类号:

TQ 028

张奇, 张睿, 郑涛, 曹欣, 刘植昌, 刘海燕, 徐春明, 张荣, 孟祥海. 基于分子模拟的新型双阳离子质子型离子液体捕集CO₂研究[J]. 化工学报, 2025, 76(2): 797-811.

Qi ZHANG, Rui ZHANG, Tao ZHENG, Xin CAO, Zhichang LIU, Haiyan LIU, Chunming XU, Rong ZHANG, Xianghai MENG. Revealing CO₂ capture by a novel dual-cation protic ionic liquid using molecular simulation[J]. CIESC Journal, 2025, 76(2): 797-811.

图/表 15

图1 DFT计算的分子模型

Fig.1 Molecular models using in DFT calculations

表1 量化计算中的主要参数

Table 1 Main parameters in quantum calculations

计算项目/方法	计算参数
functional	Perdew-Burke-Ernzerhof (PBE)
basis set	TZV2P-MOLOPT-PBE-GTH
dispersion correction	DFT-D3(BJ)
CUTOFF	400 Ry
EPS_SCF	1 × 10^-7 Ha
MAX_DR	0.003 Bohr
MAX_FORCE	0.00045 Ha/Bohr
RMS_DR	0.0015 Bohr
RMS_FORCE	0.0003 Ha/Bohr

图2 MD计算的分子模型

Fig.2 Molecular models using in MD calculations

图3 DFT计算团簇稳定构型的确定过程

Fig.3 The process of identifying stable configurations of clusters for DFT calculations

图4 体系的IGMH分析图

Fig.4 IGMH analysis plot of the systems

图5 体系的电子密度差分析

Fig.5 Electron density difference analysis plot of the systems

图6 体系的AIMD模拟

Fig.6 AIMD simulation of the systems

表2 不同阴离子-CO2系统的热力学参数对比

Table 2 Thermochemical parameters comparison of different anions-CO2 systems

种类	ΔH/(kJ·mol^-1)	ΔG/(kJ·mol^-1)
[NtBuDEA]^2- - CO₂	-98.67	-54.77
[3-MethylPyr]^- - CO₂	-75.41	-30.02
[4-MethylPyr]^- - CO₂	-74.98	-30.53
[Pyr]^- - CO₂	-72.29	-29.50
[4-BromoPyr]^- - CO₂	-53.58	-13.54
[3-PhenylPyr]^- - CO₂	-52.03	-11.72

图7 CO2的吸收情况及各组分的分布情况

Fig.7 Absorption of CO2 and distribution of each component

图8 吸收平衡后的CO2吸收量和平衡前吸收剂与CO2的相互作用能

Fig.8 The CO2 amount after absorption equilibrium and the interaction energy between the absorbent and CO2 prior to equilibrium

表3 298.15 K时不同压力条件下吸收系统气相中CO2分子的初始数量

Table 3 Initial number of CO2 molecules in gas phase for the absorption systems at various pressures conditions and at 298.15 K

初始气相压力/atm	CO₂在气相的分子数
1.5	186
2	248
2.5	310
3	372
3.5	434
4	496
5	620
6	744
8	992
10	1240

图9 298.15 K时压力对CO2吸收性能的影响

Fig.9 Effect of pressure on CO2 absorption at 298.15 K

图10 CO2在纯离子液体中的动力学性质分析

Fig.10 Analysis of the dynamical properties of CO2 in pure ionic liquid

图11 CO2在纯离子液体与含30%(质量分数)水的离子液体体系中动力学性质的比较

Fig.11 Comparison of dynamic properties of CO2 in pure ionic liquid and 30%(mass) water-containing systems

图12 CO2在纯离子液体与含30%（质量分数）水的离子液体体系中均方位移与扩散系数的比较

Fig.12 Comparison of mean square displacement and diffusion coefficient of CO2 in pure ionic liquid and 30%(mass) water-containing systems

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基于分子模拟的新型双阳离子质子型离子液体捕集CO₂研究

Revealing CO₂ capture by a novel dual-cation protic ionic liquid using molecular simulation

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