Coadsorption of CO2/CH4 onto zeolitic imidazolate frameworks: The role of inner surface polarity, framework flexibility and topology

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-03-10 DOI:10.1016/j.micromeso.2025.113557

Rimita Bose , Volodymyr Bon , Thasleem B. Nanakkal , Parasuraman Selvam , Stefan Kaskel , Niket S. Kaisare

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Abstract

The ZIF sub-family of metal-organic frameworks (MOFs) possesses considerable robustness, tunability of pores, flexibility. These properties make ZIFs potential materials for selective CO₂ adsorption from mixture of gases. However, the lack of experimental multi-component co-adsorption studies makes it challenging for translating the fundamental understanding towards large-scale separation applications. Hence, we focused on both single component adsorption and CO₂/CH₄ co-adsorption measurements. The selected frameworks include ZIF-8, ZIF-90, ZIF-7, ZIF-11 and ZIF-71, which laid the foundation of understanding the influence of functional groups, structural flexibility, crystal size and topology on CO₂ selectivity in presence of CH₄. The results indicate that polar functional group and gate-opening flexibility are a couple of key parameters to improve CO₂ selectivity for ZIFs. Topology of ZIFs, on the other hand, did not show a significant effect on CO₂ selectivity. The Ideal Adsorbed Solution Theory (IAST) is used to show the compatibility between the theoretical and experimental selectivity. The IAST exhibits mismatch for ZIF-90, indicates limitation of the theory in considering the thermodynamic analysis of framework-guest interactions. The present study highlights the factors influencing CO₂ selectivity in presence of CH₄ through both single and multi-component adsorption isotherms.

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沸石咪唑酸盐框架上的 CO2/CH4 凝聚：内表面极性、框架柔性和拓扑结构的作用

金属有机框架（MOFs）的 ZIF 子家族具有相当高的坚固性、孔隙可调性和灵活性。这些特性使 ZIFs 成为从混合气体中选择性吸附二氧化碳的潜在材料。然而，由于缺乏对多组分共吸附的实验研究，要将基本认识转化为大规模分离应用具有挑战性。因此，我们将重点放在单组分吸附和 CO2/CH4 共吸附测量上。所选框架包括 ZIF-8、ZIF-90、ZIF-7、ZIF-11 和 ZIF-71，这为了解官能团、结构灵活性、晶体尺寸和拓扑结构对 CH4 存在时 CO2 选择性的影响奠定了基础。研究结果表明，极性官能团和开栅极灵活性是提高 ZIF 的二氧化碳选择性的几个关键参数。另一方面，ZIF 的拓扑结构对 CO2 选择性没有显著影响。理想吸附溶液理论（IAST）用于显示理论与实验选择性之间的兼容性。IAST 对 ZIF-90 显示出不匹配，表明该理论在考虑框架-客体相互作用的热力学分析时存在局限性。本研究通过单组分和多组分吸附等温线，强调了在有 CH4 存在时影响 CO2 选择性的因素。

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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.