Copper-based metal–organic framework with two methane traps for efficient CH4/N2 separation

doi:10.1016/j.cjche.2024.12.002

中国化学工程学报 ›› 2025, Vol. 79 ›› Issue (3): 234-240.DOI: 10.1016/j.cjche.2024.12.002

Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation

Zhiwei Zhao¹, Yating Wang¹, Yuhao Tang¹, Xiaoqing Wang^1,2, Feifei Zhang^1,2, Jiangfeng Yang^1,2

1. College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China;
2. Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, China

收稿日期:2024-09-09 修回日期:2024-12-05 接受日期:2024-12-06 出版日期:2025-03-28 发布日期:2025-01-22
通讯作者: Feifei Zhang,E-mail:zhangfeifei0096@link.tyut.edu.cn;Jiangfeng Yang,E-mail:yangjiangfeng@tyut.edu.cn
基金资助:
The authors are thankful for the financial support from the National Natural Science Foundation of China (22408258 and 22378287), the Joint Founds of the National Natural Science Foundation of China (U20B6004), and the Natural Science Foundation of Shanxi Province (202303021222012).

Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation

Zhiwei Zhao¹, Yating Wang¹, Yuhao Tang¹, Xiaoqing Wang^1,2, Feifei Zhang^1,2, Jiangfeng Yang^1,2

1. College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China;
2. Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, China

Received:2024-09-09 Revised:2024-12-05 Accepted:2024-12-06 Online:2025-03-28 Published:2025-01-22
Supported by:
The authors are thankful for the financial support from the National Natural Science Foundation of China (22408258 and 22378287), the Joint Founds of the National Natural Science Foundation of China (U20B6004), and the Natural Science Foundation of Shanxi Province (202303021222012).

摘要/Abstract

摘要： Unconventional natural gas has become an important supplement to conventional energy sources, and the process of enrichment and purification of methane from low concentration coalbed methane is crucial. To this end, we report a copper-based metal–organic framework (MOF), ZJNU-119Cu, featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites. ZJNU-119Cu exhibits a high methane adsorption capacity (58.2 cm³·g^-1) at 298 K and 0.1 MPa and excellent CH₄/N₂ separation performance under dynamic conditions. Density-functional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH₄. The gas adsorption isotherms, heat of adsorption calculations, and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH₄/N₂ separation.

关键词: Natural gas, Adsorption, Separation, Uncoordinated carboxylic acid oxygens, Open metal sites, Methane trap

Abstract: Unconventional natural gas has become an important supplement to conventional energy sources, and the process of enrichment and purification of methane from low concentration coalbed methane is crucial. To this end, we report a copper-based metal–organic framework (MOF), ZJNU-119Cu, featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites. ZJNU-119Cu exhibits a high methane adsorption capacity (58.2 cm³·g^-1) at 298 K and 0.1 MPa and excellent CH₄/N₂ separation performance under dynamic conditions. Density-functional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH₄. The gas adsorption isotherms, heat of adsorption calculations, and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH₄/N₂ separation.

Key words: Natural gas, Adsorption, Separation, Uncoordinated carboxylic acid oxygens, Open metal sites, Methane trap

Zhiwei Zhao, Yating Wang, Yuhao Tang, Xiaoqing Wang, Feifei Zhang, Jiangfeng Yang. Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation[J]. 中国化学工程学报, 2025, 79(3): 234-240.

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Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation

Copper-based metal–organic framework with two methane traps for efficient CH₄/N₂ separation

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