Water intrusion-extrusion in 2-ethylimidazole/2-propylimidazole-doped ZIF-8: Influence of the substituent on imidazolate linker

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-06-10 DOI:10.1016/j.micromeso.2025.113728

Yifan Wang , Hao Jiang , Yousheng Zhou , Peicheng Li , Qiyue Zhao , Chuanlei Liu , Qiumin Wu , Diyi Fang , Benxian Shen , Hui Sun

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引用次数: 0

Abstract

Controlling the intrusion and extrusion of non-wetting liquids in porous materials is fundamentally important for exploring the extensive applications of heterogeneous lyophobic systems (HLSs). Among various porous materials, metal-organic frameworks (MOFs) show promising potential for constructing HLSs due to their exceptional structural tunability. However, modulating their structures while maintaining both hydrophobicity and porosity remains a great challenge. In this work, a series of linker-doped zeolitic imidazolate frameworks (ZIFs) were synthesized by incorporating two additional linkers, 2-ethylimidazole and 2-propylimidazole, into ZIF-8. Synthesized samples were thoroughly characterized and subsequently employed to investigate water intrusion-extrusion within their structures. Combined characterizations confirm that these linker-doped ZIFs exhibit tunable pore sizes and hydrophobicity. Water intrusion-extrusion experiments reveal that the intrusion pressure of the HLSs involving ZIFs can be well-tuned within the range of 26–49 MPa. Cycling intrusion-extrusion tests confirm the enhanced stability of linker-doped ZIFs. In addition, molecular dynamics simulations suggest that bulkier and more hydrophobic substituents on secondary linkers spatially hinder the diffusion of water molecules and facilitate their outflow. This study provides an approach to tuning the mechanical properties of HLSs and offers insights into the rational design of MOFs for a variety of applications.

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2-乙基咪唑/2-丙基咪唑掺杂ZIF-8的水侵挤作用：取代基对咪唑连接剂的影响

控制非润湿液体在多孔材料中的侵入和挤压对于探索非均相疏水体系（hss）的广泛应用至关重要。在各种多孔材料中，金属有机框架（mof）由于其特殊的结构可调性而显示出构建高通量系统的潜力。然而，在保持疏水性和孔隙度的同时调节它们的结构仍然是一个巨大的挑战。本研究通过在ZIF-8中加入2-乙基咪唑和2-丙基咪唑两种连接剂，合成了一系列掺杂连接剂的沸石咪唑盐框架（zif）。对合成的样品进行了彻底的表征，并随后用于研究其结构中的水侵入-挤压。综合表征证实，这些连接剂掺杂的zif具有可调节的孔径和疏水性。水侵挤实验表明，含zif的hss的侵压压力可以在26 ~ 49 MPa范围内进行很好的调节。循环侵入-挤压试验证实了掺有连接剂的zif的稳定性增强。此外，分子动力学模拟表明，二级连接体上体积更大、疏水性更强的取代基在空间上阻碍了水分子的扩散，促进了水分子的流出。该研究提供了一种调整hss力学性能的方法，并为各种应用的mof的合理设计提供了见解。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.