Adsorption dynamics of aromatic and polar volatile organic compounds on metal-organic frameworks

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-03-26 DOI:10.1016/j.micromeso.2025.113619

Sina Neshati, Zaher Hashisho

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Abstract

The study explores the effectiveness of metal-organic frameworks (MOFs) in capturing volatile organic compounds (VOCs). Specifically, it investigates the effect of polarity and aromaticity of VOCs on their adsorption behavior on two MOFs, CuBTC and FeBTC. Cyclic adsorption breakthroughs and isotherms were completed using toluene, 2-methylpyridine, n-hexane, and 2-methyl-2-butanol as adsorbates to assess the frameworks' adsorption and regeneration capabilities. X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetry analysis, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption isotherm were used to evaluate the MOFs' crystallinity, thermal stability, and surface properties. The results suggest that CuBTC demonstrates superior adsorption capabilities for all tested VOCs, due to its larger surface area and higher crystallinity. However, FeBTC has a broader pore sizes, allowing faster VOC mass transfer rates and accommodating larger molecules, albeit with slightly lower adsorption capacities. Notably, VOCs with polar and aromatic properties, such as 2-methylpyridine, exhibited higher adsorption levels due to increased π-π interactions within the frameworks. However, regeneration of 2-methylpyridine was challenging due to chemisorption, forming strong, irreversible metal–nitrogen coordination bonds. Toluene and 2-methyl-2-bustanol showed similar adsorption capacities and could be effectively regenerated, indicating physisorption mechanisms involving π–π interactions and polar interactions, respectively. N-hexane exhibited the lowest adsorption capacities, relying on weaker van der Waals forces. These results highlight the promising potential of CuBTC and FeBTC in mitigating air pollution. The research also offers valuable insights for tailoring MOFs to contaminants' molecular properties, and advances our understanding of MOF applications in air quality engineering.

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芳香族和极性挥发性有机化合物在金属-有机骨架上的吸附动力学

该研究探讨了金属有机框架（MOFs）在捕获挥发性有机化合物（VOCs）方面的有效性。具体来说，研究了极性和芳香性对VOCs在CuBTC和FeBTC两种mof上吸附行为的影响。以甲苯、2-甲基吡啶、正己烷和2-甲基-2-丁醇为吸附剂，完成了循环吸附突破和等温线，以评估框架的吸附和再生能力。采用x射线衍射、x射线光电子能谱、热重分析、傅里叶变换红外光谱和氮吸附/脱附等温线对mof的结晶度、热稳定性和表面性能进行了评价。结果表明，由于其更大的表面积和更高的结晶度，CuBTC对所有测试的voc都表现出优异的吸附能力。然而，FeBTC具有更宽的孔径，允许更快的VOC传质速率和容纳更大的分子，尽管吸附能力略低。值得注意的是，具有极性和芳香性质的挥发性有机化合物，如2-甲基吡啶，由于框架内π-π相互作用的增加，表现出更高的吸附水平。然而，由于化学吸附，2-甲基吡啶的再生具有挑战性，形成强的，不可逆的金属-氮配位键。甲苯和2-甲基-2-丁醇表现出相似的吸附能力并能有效再生，表明其物理吸附机制分别涉及π -π相互作用和极性相互作用。正己烷的吸附能力最低，依赖于较弱的范德华力。这些结果突出了CuBTC和FeBTC在缓解空气污染方面的巨大潜力。该研究还为根据污染物的分子特性定制MOF提供了有价值的见解，并促进了我们对MOF在空气质量工程中的应用的理解。

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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.