混合超微孔材料中CO2/N2吸附与分离的理论研究

doi:10.15541/jim20190214

摘要/Abstract

摘要：

碳捕获与封存技术是一种具有前景的CO₂减排策略。本工作采用巨正则蒙特卡洛模拟研究了温度为298 K、压强在0~5 kPa范围内三种混合超微孔材料SIFSIX-X-Cu(以SiF₆ ^2-排列, Cu为金属中心, X=2, 3, O)中CO₂/N₂吸附与分离的行为。结果显示, 相比于SIFSIX-2-Cu, SIFSIX-3-Cu和SIFSIX-O-Cu中CO₂在0.5 kPa就达到吸附饱和, 且在1 kPa下的吸附量分别达到了2.70与2.39 mmol·g ^-1。CO₂/N₂混合气体中CO₂的吸附量几乎没有下降。SIFSIX-3-Cu和SIFSIX-O-Cu具有接近于CO₂分子动力学直径的孔径, 对CO₂亲和力较大, 吸附热分别达到了59和66 kJ·mol ^-1。密度泛函理论分析发现, 在两种结构中每个孔隙只吸附一个CO₂分子, 且几乎处于孔道的中心。本工作为低压下吸附与分离CO₂的混合超微孔材料的开发提供了理论指导。

关键词: 巨正则蒙特卡洛, 混合超微孔材料, 吸附, 分离

Abstract:

Carbon capture and storage (CCS) is a promising strategy for reduction of CO₂ emissions. Herein, CO₂/N₂ adsorption and separation in three SIFSIX-X-Cu (arrayed via SiF₆ ^2- with Cu metal center, X = 2, 3, O) hybrid ultramicroporous materials at 298 K within 0-5 kPa were investigated by using grand canonical Monte Carlo (GCMC) simulation. Results showed that, in contrast to SIFSIX-2-Cu, CO₂ adsorption in SIFSIX-3-Cu and SIFSIX-O-Cu reached saturation at 0.5 kPa and their CO₂ adsorption capacity were 2.70 and 2.39 mmol·g ^-1 at 1 kPa, respectively. The CO₂ adsorption capacity in CO₂/N₂ mixture barely decreased. SIFSIX-3-Cu and SIFSIX-O-Cu owned close pore sizes to CO₂ dynamics diameter, thereby exhibiting high CO₂ affinity with adsorption heat of 59 and 66 kJ·mol ^-1, respectively. Density functional theory (DFT) analyses showed only one CO₂ molecule could be adsorbed in each hole and located at the center of SIFSIX-3-Cu and SIFSIX-O-Cu. Our results provide a theoretical guidance for developing ultramicroporous materials in adsorption and separation of CO₂ at low pressure.

Key words: grand-canonical Monte Carlo, hybrid microporous materials, adsorption, separation

中图分类号:

O611

鲁效庆,王茂槐. 混合超微孔材料中CO₂/N₂吸附与分离的理论研究[J]. 无机材料学报, 2020, 35(4): 469-474.

LU Xiaoqing,WANG Maohuai. Theoretical Investigation on Adsorption and Separation of CO₂/N₂ in Hybrid Ultramicroporous Materials[J]. Journal of Inorganic Materials, 2020, 35(4): 469-474.

图/表 8

图1 (a) SIFSIX-3-Cu、(b) SIFSIX-2-Cu和(c) SIFSIX-O-Cu的SIFSIX-X-Cu结构

Fig. 1 Structures of SIFSIX-X-Cu: (a) SIFSIX-3-Cu; (b) SIFSIX-2-Cu; (c) SIFSIX-O-Cu

表1 SIFSIX-X-Cu结构的孔隙结构物理特性

Table 1 Physical characteristics of SIFSIX-X-Cu

	V_P/(cm³·g^-1)	D/nm	Porosity, Φ/%	Surface area, A/(m²·g^-1)
SIFSIX-3-Cu	0.27	0.34	32.48	300
SIFSIX-2-Cu	0.40	0.52	35.70	735
SIFSIX-O-Cu	0.22	0.34	37.00	300

图2 298 K下SIFSIX-X-Cu中CO2 (a)和N2 (b)的吸附等温线

Fig. 2 Adsorption isotherms of CO2 (a) and N2 (b) in SIFSIX-X-Cu at 298 K

图3 298 K下(a)SIFSIX-3-Cu, (b)SIFSIX-2-Cu, (c)SIFSIX-O-Cu中CO2/N2单组份与混合组份的吸附等温线

Fig. 3 Adsorption isotherms of single component and mixture of CO2/N2 in (a) SIFSIX-3-Cu, (b) SIFSIX-2-Cu, and (c) SIFSIX-O-Cu at 298 K

图4 (a) CO2与(b) N2在SIFSIX-X-Cu中的吸附热

Fig. 4 Isosteric heat of (a) CO2 and (b) N2 in SIFSIX-X-Cu

图5 SIFSIX-3-Cu (a-俯视图, c-侧视图)和SIFSIX-O-Cu (b-俯视图, d-侧视图)中CO2的吸附位点

Fig. 5 CO2 adsorption sites in SIFSIX-3-Cu (a-top view, c-side view) and SIFSIX-O-Cu (b-top view, d-side view)

图6 (a) SIFSIX-3-Cu和(b) SIFSIX-O-Cu中CO2的最稳定吸附位点

Fig. 6 The most stable CO2 adsorption sites in (a) SIFSIX-3-Cu and (b) SIFSIX-O-Cu

图7 CO2与骨架Si原子之间的径向分布函数

Fig. 7 Radial distribution functions of CO2 around Si atoms in frameworks

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混合超微孔材料中CO₂/N₂吸附与分离的理论研究

Theoretical Investigation on Adsorption and Separation of CO₂/N₂ in Hybrid Ultramicroporous Materials

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