Molecular simulation study on CO2/N2 separation via 3D-contorted catalytic arene-norbornene annulation polymer membrane

doi:10.11949/0438-1157.20241220

Abstract

Abstract:

Membrane separation is an efficient and energy-saving CO₂ separation technology. Intrinsic microporous ladder polymers are regarded as the superior materials for CO₂ separation technology due to their high porosity, high selectivity and stable structure. In this work, based on molecular dynamics simulation, a 3D-contorted CANAL ladder polymer membrane (named CANAL-Me-S5F membrane) is constructed, and the sorption as well as permeation performance of CO₂/N₂ mixture are investigated. To fully consider the flexibility of polymer membrane, most polymer chains can freely move during the simulation. The results show that the adsorption quantity of CO₂ in the membrane (4.00 mmol/g) is significantly larger than that of N₂(0.30 mmol/g), which is mainly caused by the stronger interaction between CO₂ and membrane. The permeabilities of CO₂ and N₂ through the CANAL-Me-S5F membrane are 22546.09 Barrer and 1094.01 Barrer, respectively. The permselectivity $α P (C O 2 / N 2)$ (20.61) is in good agreement with reported experiment. The CANAL-Me-S5F membrane exhibits high permeability selectivity for CO₂ molecules, mainly due to the high solubility (i.e., preferential adsorption) of CO₂ in the membrane material. The research results provide theoretical support for the design and development of new polymer membranes for gas separati on.

Key words: ladder polymers of intrinsic microporosity, CO₂/N₂separation, membrane, separation, molecular simulation

摘要：

膜分离技术是一种高效、节能的CO₂分离技术。固有微孔梯形聚合物因其高孔隙率、高选择性、结构稳定等优点被视作CO₂分离技术的优势材料。通过分子动力学模拟方法构建了三维扭曲催化芳烃-降冰片烯环化（CANAL）梯形聚合物膜（CANAL-Me-S5F膜）对CO₂/N₂混合气体的吸附和渗透模型，并对其CO₂/N₂分离性能进行研究。为了充分考虑聚合物链的柔性特征，在计算过程中，聚合物膜的大部分结构保持自由运动状态。结果表明，CO₂在CANAL-Me-S5F膜中的吸附量（4.00 mmol/g）明显大于N₂（0.30 mmol/g），这是由CANAL-Me-S5F与CO₂分子之间更强的相互吸引作用决定的。CANAL-Me-S5F膜中CO₂和N₂的渗透率分别为22546.09 Barrer和1094.01 Barrer，渗透选择性 $α P (C O 2 / N 2)$ 为20.61，该渗透选择性与已报道的实验数值十分吻合。CANAL-Me-S5F膜对CO₂分子呈现出较高的渗透选择性，主要是由CO₂在膜材料中的高溶解度（即优先吸附）主导的。研究结果可从微观层面为新型气体分离聚合物膜的设计与开发提供理论支撑。

关键词: 固有梯形聚合物, CO₂/N₂分离, 膜, 分离, 分子模拟

CLC Number:

TQ 028.8

Zijuan LI, Xiaoyan TAN, Yongsheng WU, Chenyi YANG, Hong CHEN, Xiaogang BI, Jie LIU, Faquan YU. Molecular simulation study on CO₂/N₂ separation via 3D-contorted catalytic arene-norbornene annulation polymer membrane[J]. CIESC Journal, 2025, 76(5): 2348-2357.

李紫鹃, 谭晓艳, 吴永盛, 杨陈怡, 陈红, 毕小刚, 刘捷, 喻发全. 分子模拟研究三维扭曲催化芳烃-降冰片烯环化聚合物膜的CO₂/N₂分离机理[J]. 化工学报, 2025, 76(5): 2348-2357.

Figures/Tables 9

Fig.1 Structure of CANAL-Me-S5F polymer （a） and sorption （b） and permeation（c） processes of CO2/N2 mixture （purple area in membrane refers to restrained layer）

Fig.2 Variation of gas adsorption capacity in CANAL-Me-S5F membrane with time during adsorption process

Table 1 Results of gas separation through CANAL-Me-S5F membrane

参数	气体	模拟值	现有文献结果 ^[23]
S/（mmol/g）	CO₂	4.00	—
S/（mmol/g）	N₂	0.30	—
$α S (C O 2 / N 2)$		13.33	—
P/Barrer	CO₂	22546.09	4000±100
P/Barrer	N₂	1094.01	220±8
$α P (C O 2 / N 2)$		20.61	18

Table 1 Results of gas separation through CANAL-Me-S5F membrane

参数	气体	模拟值	现有文献结果 ^[23]
S/（mmol/g）	CO₂	4.00	—
S/（mmol/g）	N₂	0.30	—
$α S (C O 2 / N 2)$		13.33	—
P/Barrer	CO₂	22546.09	4000±100
P/Barrer	N₂	1094.01	220±8
$α P (C O 2 / N 2)$		20.61	18

Fig.3 Interaction energies between gas molecules and polymeric membrane

Fig.4 Radial distribution function of CO2 and N2 molecules around atoms of CANAL-Me-S5F polymer

Fig.5 Free volumes for dense membrane and membranes after gas sorption

Fig.6 Variation of number of gas molecules sorbed in CANAL-Me-S5F membrane and permeated through CANAL-Me-S5F membrane versus time during permeation

Fig.7 Density profiles of CO2 and N2 along z direction during sorption （a） and permeation （b） processes （membrane is between the two dashed lines）

Fig.8 Mean-squared displacements of gas molecules in membranes along z direction

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Molecular simulation study on CO₂/N₂ separation via 3D-contorted catalytic arene-norbornene annulation polymer membrane

分子模拟研究三维扭曲催化芳烃-降冰片烯环化聚合物膜的CO₂/N₂分离机理

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