广西师范大学学报（自然科学版） ›› 2026, Vol. 44 ›› Issue (2): 211-217.doi: 10.16088/j.issn.1001-6600.2025031301

• 化学与材料科学 • 上一篇    下一篇

稳定簇基MOF中[Cu10O(OH)12]6+与无序SiF2-6动态关联影响选择性吸附

石磊1, 董求兵2*, 曾明华1,3,4*   

  1. 1.湖北大学 化学化工学院,湖北 武汉 430062;
    2.安徽师范大学 化学与材料科学学院,安徽 芜湖 241000;
    3.广西师范大学 化学与药学学院,广西 桂林 541004;
    4.省部共建药用资源化学与药物分子工程国家重点实验室(广西师范大学),广西 桂林 541004
  • 收稿日期:2025-03-13 修回日期:2025-05-04 出版日期:2026-03-05 发布日期:2026-02-03
  • 通讯作者: 曾明华(1972—),男,湖南邵阳人,广西师范大学教授,博导。E-mail: zmh@mailbox.gxnu.edu.cn; 董求兵(1996—),男,安徽安庆人,安徽师范大学副教授,博士。E-mail: dongqiubing@ahnu.edu.cn
  • 基金资助:
    国家自然科学基金(U23A2080, 22171075, 22401005)

Dynamic Correlation Between [Cu10O(OH)12]6+ and Disordered SiF2-6in Stable Cluster-based MOF and Implications for Selective Adsorption

SHI Lei1, DONG Qiubin2*, ZENG Minghua1,3,4*   

  1. 1. School of Chemistry and Chemical Engineering, Hubei University, Wuhan Hubei 430062, China;
    2. College of Chemistry and Materials Science, Anhui Normal University, Wuhu Anhui 241000, China;
    3. School of Chemistry and Pharmacy Science, Guangxi Normal University, Guilin Guangxi 541004, China;
    4. State Key Laboratory For Chemistry and Molecular Engineering of Medicinal Resources(Guangxi Normal University), Guilin Guangxi 541004
  • Received:2025-03-13 Revised:2025-05-04 Online:2026-03-05 Published:2026-02-03

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摘要： 本文以水热稳定的铜簇基金属-有机框架材料{[Cu10(μ6-O)(μ3-OH)12(dip)4(H2O)4](H2O)13H2(SiF6)4} (NTU-85)为研究对象,重点探究SiF2-6作为动态抗衡离子的功能特性。单晶结构分析表明,其孔道中SiF2-6阴离子被Cu10簇中的μ3-OH协同孔内晶格水分子和配位水分子以氢键方式固定。加热去除晶格水和配位水后,SiF2-6失去与晶格水及配位水的氢键作用而展示出无序态,但仍与Cu簇保持弱作用并形成动态关联,在葫芦状的微孔(0.48~0.83 nm)环境内充当动态性的电负性识别位点。在OH-位点以及动态SiF2-6的协同作用下,这种复合孔系统在298 K下对可极化的气体小分子表现出优越的吸附性能,如乙炔40.0 cm3/g,二氧化碳36.5 cm3/g,而对具有低可极化率和非极性气体分子展现较低吸附能力,如乙烯24.3 cm3/g、甲烷8.7 cm3/g,氮气1.6 cm3/g。理想吸附溶液理论(IAST)评估了C2H2/C2H4、CO2/CH4和CO2/N2的选择性值分别为12.7、70.1、34.7,表明动态的抗衡SiF2-6离子通过局部静电相互作用或偶极-四极作用对可极化乙炔和二氧化碳具有选择性吸附作用,对极性气体分离技术发展具有一定参考价值。

关键词: 稳定簇基MOF, [Cu10O(OH)12]6+核, SiF2-6抗衡离子, 动态关联, 选择性吸附

Abstract: This study focuses on investigating the functional characteristics of SiF2-6 as a dynamic counterion in a hydrothermally stable copper-cluster-based metal organic framework(MOF) [Cu10(μ6-O)(μ3-OH)12(dip)4 (H2O)4](H2O)13H2(SiF6)4(NTU-85). Single-crystal X-ray diffraction analysis reveals that the SiF2-6 anions in the channels are anchored via hydrogen-bonding networks formed by μ3-OH groups of the Cu10 clusters, lattice water molecules, and coordinated water molecules. Upon thermal removal of lattice and coordinated water molecules, the SiF2-6 anions lose hydrogen bonding interactions with these water species, adopting a disordered state while maintaining weak interactions with the Cu clusters, thereby forming a dynamic association. Within the gourd-shaped micropores (0.48~0.83 nm), these anions function as dynamic electronegative recognition sites. Under the synergistic effects of exposed OH- groups and the dynamic SiF2-6 anions, this composite pore system exhibits exceptional adsorption performance at 298 K for polarizable small gas molecules, with uptake capacities of 40.0 cm3/g (C2H2) and 36.5 cm3/g (CO2), and lower uptake for the gas with low polarizability or nonpolar gas, such as C2H4 (24.3 cm3/g), CH4 (8.7 cm3/g), and N2 (1.6 cm3/g) at 298 K. Remarkable selectivities of C2H2/C2H4 (12.7), CO2/CH4 (70.1), and CO2/N2 (34.7) were evaluated by the ideal adsorption solution theory (IAST), which highlights the critical role of counterion SiF2-6 in the capture of polarizable C2H2 and CO2 via localized electrostatic interactions or dipole-quadrupole interaction. It has certain reference value for the development of polar gas separation technology.

Key words: stable cluster-based MOF, [Cu10O(OH)12]6+ core, SiF2-6 counter-ion, dynamic correlation, selective adsorption

中图分类号:  TQ051.8;O647.3

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