化工新型材料

化工新型材料 ›› 2025, Vol. 53 ›› Issue (8) : 192-196. DOI: 10.19817/j.cnki.issn1006-3536.2025.08.049

科学研究

金属有机骨架中官能团对CO₂/N₂吸附分离性能的影响

^1,2*

^1,2

作者信息 +

Effect of functional groups in metal-organic framework on the adsorption and separation performance of CO₂/N₂

He Mengfan¹, Liu Xiuying^1,2, Du Kun¹, Huang Jilong¹, Yu Jingxin^1,2, Li Xiaodong^1,2

Author information +

文章历史 +

Received		Published
2024-12-17		2025-08-20
Issue Date	Revised Date
2025-08-15	2024-12-17

PDF

摘要

使用巨正则蒙特卡罗方法(GCMC)研究了经过4种官能团(—CH₃、—OH、—NH₂、—O—Li)修饰过的Ni-MOF-74和未被修饰的Ni-MOF-74这5种金属有机骨架(MOFs)对CO₂和N₂的吸附与分离性能,获得了它们对CO₂和N₂分子的单组分吸附、混合组分吸附、等量吸附热以及混合组分时的吸附选择性等性能,并对这5种材料的吸附与分离性能进行了对比研究。结果表明:在单组分吸附中,官能团修饰的MOFs对CO₂和N₂的吸附热均大于未被官能团修饰过的Ni-MOF-74,显示出官能团的引入能有效增强气体的吸附能力。在0～6bar时吸附热对吸附量的影响较大,随着压力的增加,孔隙体积效应成为影响吸附性能的关键因素,具有更大孔体积和比表面积的Ni-MOF-74对CO₂的吸附容量明显提高,最后反超其他4种被官能团修饰的MOFs。在混合组分吸附中,经过官能团修饰的MOFs对CO₂的吸附容量和选择性均高于未被官能团修饰的Ni-MOF-74。其中CH₃-Ni-MOF-74和OH-Ni-MOF-74对CO₂的吸附选择性最好,表明这些官能团在提高CO₂吸附效率和选择性方面具有重要作用。

Abstract

The gas adsorption and separation performance of five metal-organic frameworks (MOFs),namely Ni-MOF-74 modified with four functional groups (—CH₃,—OH,—NH₂,—O—Li) and unmodified Ni-MOF-74,towards CO₂ and N₂ were investigated using grand canonical Monte Carlo (GCMC) simulations.The single-component adsorption,mixed-component adsorption,isosteric heat of adsorption,and adsorption selectivity of these materials towards CO₂ and N₂ molecules were obtained.The adsorption and separation performance of these five materials were compared.The results showed that,in single-component adsorption,the modified MOFs with functional groups exhibited higher isosteric heat of adsorption for CO₂ and N₂ compared to unmodified Ni-MOF-74,indicating that the introduction of functional groups could effectively enhance the gas adsorption capacity of MOFs.At pressures ranging from 0 to 6 bar,the isosteric heat of adsorption had a greater impact on the adsorption capacity.As the pressure increased,the pore volume effect became a key factor affecting the adsorption performance.Ni-MOF-74 with larger pore volume and surface area showed a significant increase in CO₂ adsorption capacity,surpassing the other four functionalized MOFs.In mixed-component adsorption,the modified MOFs exhibited higher CO₂ adsorption capacity and selectivity than unmodified Ni-MOF-74.Among them,CH₃-Ni-MOF-74 and OH-Ni-MOF-74 showed the best adsorption selectivity for CO₂,indicating the important role of these functional groups in improving CO₂ adsorption efficiency and selectivity.

关键词

吸附 / 分离 / CO₂和N₂ / 巨正则蒙特卡洛模拟

Key words

adsorption / separation / CO₂/N₂ / grand canonical Monte Carlo simulations

引用本文

引用格式 ▾

金属有机骨架中官能团对CO₂/N₂吸附分离性能的影响[J]. 化工新型材料, 2025, 53(8): 192-196 DOI:10.19817/j.cnki.issn1006-3536.2025.08.049

登录浏览全文

4963

注册一个新账户忘记密码

参考文献

原文顺序 | 出版日期 | 本文引用

[1] 鲁博文,张立麒,徐勇庆,等.碳捕集、利用与封存(CCUS)技术助力碳中和实现[J].工业安全与环保,2021,47(S1):30-34.
[2] 李佳,苗萌,潘洪志.金属有机骨架材料在吸附分离大气污染物中的应用[J].分析试验室,2022,41(2):225-231.
[3] Pahinkar D G,Garimella S.A novel temperature swing adsorption process for natural gas purification:part I,model development[J].Separation and Purification Technology,2018,203:124-142.
[4] 刘振翼,李嘉璐,李鹏亮,等.高温高压下N₂和CO₂对CH₄/C₂H₆/C₃H₈混合气抑爆效果研究[J].北京理工大学学报自然版,2023,43(2):111-117.
[5] Yuan B,Wu X,Chen Y,et al.Adsorption of CO₂,CH₄,and N₂ on ordered mesoporous carbon:approach for greenhouse gases capture and biogas upgrading[J].Environmental Science & Technology,2013,47(10):5474-5480.
[6] Alhamami M,Doan H,Cheng C.A review on breathing behaviors of metal-organic-frameworks(MOFs) for gas adsorption[J].Materials,2014,7(4):3198-3250.
[7] Lee J Y,Farha O K,Roberts J,et al.Metal-organic framework materials as catalysts[J].Chemical Society Reviews,2009,38(5):1450-1459.
[8] 赵杰,刘森,殷齐康,等.三角形MOF孔道中CO₂捕获分离:孔径尺寸和官能团数量的影响[J].化工新型材料,2024,52(S1):223-228,235.
[9] Lin Y,Kong C,Zhang Q,et al.Metal-organic frameworks for carbon dioxide capture and methane storage[J].Advanced Energy Materials,2017,7(4):1601296.
[10] Chen S,Li X,Duan J,et al.Investigation of highly efficient adsorbent based on Ni-MOF-74 in the separation of CO₂ from natural gas[J].Chemical Engineering Journal,2021,419:129653.
[11] Zhang Y,Hu G,Gao X,et al.Simulation study on functional group-modified Ni-MOF-74 for CH₄/N₂ adsorption separation[J].Journal of Computational Chemistry,2024,45(17):1515-1524.
[12] Rappe A K,Casewit C J,Colwell K S,et al.UFF,a full periodic table force field for molecular mechanics and molecular dynamics simulations[J].Journal of the American Chemical Society,1992,114(25):10024-10035.
[13] Mayo S L,Olafson B D,Goddard W A.A generic force field for molecular simulations[J].Journal of Physical Chemistry,1990,94(26):8897-8909.
[14] Dubbeldam D,Torres-Knoop A,Walton K S.On the inner workings of Monte Carlo codes[J].Molecular Simulation,2013,39(14-15):1253-1292.
[15] Dubbeldam D,Calero S,Ellis E D,et al.RASPA:molecular simulation software for adsorption and diffusion in flexible nanoporous materials[J].Molecular Simulation,2016,42(2):81-101.
[16] Vlugt T J H,García-Pérez E,Dubbeldam D,et al.Computing the heat of adsorption using molecular simulations:the effect of strong Coulombic interactions[J].Journal of chemical theory and computation,2008,4(7):1107-1118.
[17] 刘秀英,李晓凤,张丽英,等.甲烷在不同分子筛中吸附的理论对比研究[J].物理学报,2012,61(15):146802(1-7).
[18] Jiang J.Molecular simulations in metal-organic frameworks for diverse potential applications[J].Molecular Simulation,2014,40(7-9):516-536.