金属有机框架材料中CO2/N2吸附与分离的理论研究

doi:10.15541/jim20190290

无机材料学报 ›› 2020, Vol. 35 ›› Issue (6): 697-702.DOI: 10.15541/jim20190290 CSTR: 32189.14.10.15541/jim20190290

金属有机框架材料中CO₂/N₂吸附与分离的理论研究

翟婉如¹,王佳惠¹,王茂槐¹,杜雪梅¹,魏淑贤²()

^1. 材料科学与工程学院中国石油大学(华东), 青岛 266580
^2. 理学院中国石油大学(华东), 青岛 266580

收稿日期:2019-06-13 修回日期:2019-07-08 出版日期:2020-06-20 网络出版日期:2019-07-23
作者简介:翟婉如(1997-), 女, 本科生. E-mail: 944415335@qq.com;
ZHAI Wanru(1997-), wale,undergraduate. E-mail: 944415335@qq.com
基金资助:
山东省自然科学基金(ZR2017MA024);山东省自然科学基金(ZR2019MEM005);中央高校自主创新项目(18CX02042A);中央高校自主创新项目(18CX07002A);中央高校自主创新项目(18CX05011A)

Adsorption and Separation of CO₂/N₂ in Metal Organic Frameworks: a Theoretical Investigation

ZHAI Wanru¹,WANG Jiahui¹,WANG Maohuai¹,DU Xuemei¹,WEI Shuxian²()

^1. School of Materials Science and Engineering, China University of Petroleum, Qingdao 266580, China
^2. College of Science, China University of Petroleum, China University of Petroleum, Qingdao 266580, China

Received:2019-06-13 Revised:2019-07-08 Published:2020-06-20 Online:2019-07-23
Supported by:
Shandong Natural Science Foundation, China(ZR2017MA024);Shandong Natural Science Foundation, China(ZR2019MEM005);Fundamental Research Funds for the Central Universities, China(18CX02042A);Fundamental Research Funds for the Central Universities, China(18CX07002A);Fundamental Research Funds for the Central Universities, China(18CX05011A)

摘要/Abstract

摘要：

金属有机框架(MOFs)材料在CO₂的捕获与分离方面受到广泛关注。本工作结合分子动力学(MD)和巨正则蒙特卡洛(GCMC)模拟方法探究了一种MOFs材料DUT-49的负性气体吸附过程及结构转变对CO₂/N₂吸附分离行为的影响。结果表明: 在20~60 MPa的压强下, DUT-49均发生可稳定存在的结构变形, 实现开孔(DUT-49-op)和闭孔(DUT-49-cp)状态的转变。DUT-49气体吸附量随温度升高而下降。DUT-49-cp的框架收缩, 气体有效吸附位点减少, 吸附量明显降低。此外, 与DUT-49-op相比, DUT-49-cp中CO₂/N₂选择性明显降低, 且随温度升高而下降, 不利于气体分离。本工作的研究结果为吸附剂材料的开发提供了科学依据。

关键词: 金属有机框架, 结构转变, 气体吸附与分离

Abstract:

Metal organic frameworks (MOFs) materials have received extensive attention in capture and separation of CO₂. Herein, molecular dynamic simulation (MD) and grand canonical Monte Carlo (GCMC) simulation were used to investigate the process of negative gas adsorption to DUT-49, an MOF, and the effect of structural transition on the CO₂/N₂ adsorption and separation behavior. Results showed that DUT-49 underwent stable structural deformation at 20-60 MPa, with a transition between open pore (DUT-49-op) and closed pore (DUT-49-cp). Its adsorption capacity decreased with the increase of temperature. DUT-49-cp owned a contractive framework, exhibiting a considerably decreasing adsorption capacity due to reduction of effective adsorption sites. In addition, its selectivity decreased significantly compared with that of DUT-49-op, and decreased with increase of temperature, which is not conducive to gas separation. The present study provides a scientific basis for the development of adsorbent materials.

Key words: metal organic framework, structural transition, gas adsorption and separation

中图分类号:

O611.3

翟婉如,王佳惠,王茂槐,杜雪梅,魏淑贤. 金属有机框架材料中CO₂/N₂吸附与分离的理论研究[J]. 无机材料学报, 2020, 35(6): 697-702.

ZHAI Wanru,WANG Jiahui,WANG Maohuai,DU Xuemei,WEI Shuxian. Adsorption and Separation of CO₂/N₂ in Metal Organic Frameworks: a Theoretical Investigation[J]. Journal of Inorganic Materials, 2020, 35(6): 697-702.

图/表 8

图1 DUT-49晶体结构

Fig. 1 Crystal structure of DUT-49

图2 不同压强下DUT-49的结构转变过程

Fig. 2 Structural transformation process of DUT-49 at different pressures (a) 20 MPa; (b) 30 MPa; (c) 40 MPa; (d) 50 MPa; (e) 60 MPa

图3 DUT-49结构在(a) 20、(b) 30、(c) 40、(d) 50和(e) 60 MPa下转变过程中的能量变化和(f)体积变化

Fig. 3 Energy changes at (a) 20, (b) 30, (c) 40, (d) 50 and (e) 60 MPa and (f) volume changes at 20-60 MPa in the structure transformation process of DUT-49

图4 孔径尺寸分布图

Fig. 4 Aperture size distribution

图5 (a, b)DUT-49-op和(c, d)DUT-49-cp对单组份CO2/N2吸附的等温线

Fig. 5 Adsorption isotherms of single component CO2/N2 (a, b) DUT-49-op; (c, d) DUT-49-cp

图6 (a)DUT-49-op和(b)DUT-49-cp对混合组份的选择性曲线

Fig. 6 Selectivity curves of (a) DUT-49-op and (b) DUT-49-cp for mixed components

图7 气体(a)CO2和(b)N2吸附的Snapshot图

Fig. 7 Snapshot images of gas adsorption of (a) CO2 and (b) N2

图8 (a)DUT-49-op和(b)DUT-49-cp的 CO2/N2吸附热曲线

Fig. 8 Adsorption heat curves of CO2/N2 in (a) DUT-49-op and (b) DUT-49-cp

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金属有机框架材料中CO₂/N₂吸附与分离的理论研究

Adsorption and Separation of CO₂/N₂ in Metal Organic Frameworks: a Theoretical Investigation

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