π-Quadrupole-driven gate-opening in ZIFs for selective VOC capture

IF 3.1 4区工程技术 Q3 CHEMISTRY, PHYSICAL

Adsorption Pub Date : 2025-09-26 DOI:10.1007/s10450-025-00654-z

Kevin Dedecker, Martin Drobek, Anne Julbe

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引用次数: 0

Abstract

The selective capture of volatile organic compounds (VOCs) is a significant challenge in environmental remediation. In this study, we explore how MOF structural flexibility and the electronic properties of VOCs influence their adsorption by comparing two functionalized zeolitic imidazolate frameworks: the flexible ZIF-8_CH₃ and the rigid ZIF-8_Br. Using benzene and hexafluorobenzene as probe molecules with contrasting quadrupole moments, we demonstrate that ligand functionalization significantly impacts both structural dynamics and adsorption/separation performance. ZIF-8_CH₃ exhibits higher overall uptake capacities, reaching up to 7.3 mmol/g for hexafluorobenzene. In contrast, ZIF-8_Br shows superior separation capabilities, with IAST selectivity values reaching 17.1 for benzene/hexafluorobenzene mixtures at low pressures. Our experimental and computational analyses reveal that aromatics with negative quadrupole moments more readily appear to trigger the gate-opening phenomenon, establishing a potential correlation direct correlation between electron density distribution and molecular sieving efficiency. These findings offer new insights into the rational design of functionalized frameworks for selective VOC capture, highlighting the crucial role of electronic effects in determining host-guest interactions and separation performance.

Graphical abstract

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zif中π-四极驱动的栅极开启，用于选择性捕获VOC

挥发性有机化合物（VOCs）的选择性捕获是环境修复中的一个重大挑战。在这项研究中，我们通过比较两种功能化的分子筛咪唑盐框架：柔性的ZIF-8_CH3和刚性的ZIF-8_Br，探讨了MOF的结构灵活性和电子性质对VOCs吸附的影响。以苯和六氟苯为探针分子，通过对比四极矩，我们证明了配体功能化对结构动力学和吸附/分离性能的显著影响。ZIF-8_CH3对六氟苯的吸收能力较高，达到7.3 mmol/g。相比之下，ZIF-8_Br表现出优异的分离能力，在低压下对苯/六氟苯混合物的IAST选择性值达到17.1。我们的实验和计算分析表明，负四极矩的芳烃更容易触发门打开现象，建立了电子密度分布与分子筛效率之间的潜在相关性。这些发现为选择性捕获VOC的功能化框架的合理设计提供了新的见解，强调了电子效应在决定主客体相互作用和分离性能方面的关键作用。图形抽象

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Adsorption 工程技术-工程：化工

CiteScore

8.10

自引率

3.00%

发文量

审稿时长

2.4 months

期刊介绍： The journal Adsorption provides authoritative information on adsorption and allied fields to scientists, engineers, and technologists throughout the world. The information takes the form of peer-reviewed articles, R&D notes, topical review papers, tutorial papers, book reviews, meeting announcements, and news. Coverage includes fundamental and practical aspects of adsorption: mathematics, thermodynamics, chemistry, and physics, as well as processes, applications, models engineering, and equipment design. Among the topics are Adsorbents: new materials, new synthesis techniques, characterization of structure and properties, and applications; Equilibria: novel theories or semi-empirical models, experimental data, and new measurement methods; Kinetics: new models, experimental data, and measurement methods. Processes: chemical, biochemical, environmental, and other applications, purification or bulk separation, fixed bed or moving bed systems, simulations, experiments, and design procedures.