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贾晓霞1,2 王丽1,2 元宁1,2 杨江峰1,2 李晋平1,2

(1.太原理工大学化学化工学院精细化工研究所, 山西太原 030024)
(2.气体能源高效清洁利用山西省重点实验室, 山西太原 030024)

【摘要】基于金属有机骨架材料中金属空配位对气体的强吸附作用, 利用具有较高活性的二价金属Cr2+/Mo2+/Ni2+与均苯三酸 (H3BTC) 配位合成了HKUST-1 (Cu-BTC) 同构系列材料M-BTC (M=Cr、Mo、Ni) , 并与Cu-BTC对比分析了该类型材料中不同金属空配位对甲烷和氮气的吸附性能。实验结果显示, 此三种材料均具有较好的甲烷选择吸附性, 其中含Ni2+金属空位的Ni-BTC以其尤为突出的甲烷吸附热值而呈现较好的CH4/N2分离潜力;Cr2+空配位虽具有较强活性, 但是对于甲烷的选择性吸附性能却低于含Cu2+空位的Cu-BTC材料。结合吸附选择性IAST计算分析得到此三种含较高活性不饱和金属空配位的MOFs材料对于甲烷选择性吸附作用能顺序为:Ni-BTC>Mo-BTC>Cu-BTC>Cr-BTC。

【关键词】 甲烷;氮气;吸附;吸附剂;不饱和金属空配位;


【基金资助】 国家自然科学基金项目 (51672186, 21676175) ;

CH4/N2 adsorption separation research of MOFs with divalent Cr/Mo/Ni unsaturated metal sites

JIA Xiaoxia1,2 WANG Li1,2 YUAN Ning1,2 YANG Jiangfeng1,2 LI Jinping1,2

(1.College of Chemistry and Chemical Engineering, Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, Shanxi, China 030024)
(2.Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan, Shanxi, China 030024)

【Abstract】Based on the strong interaction energy between the coordinatively unsaturated metal sites (UMSs) and the gas molecules, M-BTC (M = Cr, Mo, Ni), isostructural with HKUST-1 (Cu-BTC), were successfully synthesized via the coordination reaction of the high-activity divalent metal (Cr2+/Mo2+/Ni2+) and organic ligand (H3BTC), and then the impact of gas–metal interactions on the selective adsorption of CH4 from N2 was investigated by comparing with classical materials (Cu-BTC). The results show the good CH4 selective adsorption properties of M-BTC (M = Cr, Mo, Ni) with UMSs. Among these materials, Ni-BTC with unsaturated Ni2+ sites presents the highest adsorption heat value for CH4, leading to the excellent CH4/N2 adsorption separation properties; but the Cr-BTC with high Cr2+ activity shows the lower ability for CH4/N2 separation than Cu-BTC. Taking into consideration the IAST calculation results, we verified the ability for the selective adsorption of CH4 molecules on M-BTC (M = Cr, Mo, Ni) and Cu-BTC followed as Ni-BTC > Mo-BTC > Cu-BTC > Cr-BTC.

【Keywords】 methane; nitrogen; adsorption; adsorbents; coordinatively unsaturated metal sites;


【Funds】 National Natural Science Foundation of China (51672186, 21676175) ;

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This Article


CN: 11-1946/TQ

Vol 69, No. 09, Pages 3896-3904+4138

September 2018


Article Outline


  • Introduction
  • 1 Experimental materials and methods
  • 2 Experimental results and discussion
  • 3 Conclusion
  • References