稳定性和疏水性优异的后改性氟官能化共价有机骨架及其在氟虫腈吸附中的应用

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-05-29 DOI:10.1016/j.micromeso.2025.113710

Pengda Hu , Xiaoli Ma , Ruixia Yang , Xiaoyan Zhang , Xiaoyu Huang , Hua Yuan , Qiaohong Peng

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引用次数: 0

摘要

通过合成后Povarov反应，设计并合成了两种氟功能化共价有机框架（F-COFs）： tpt - dhta - cof -(CF3)和tpt - dhta - cof - 3f。亚胺键不可逆地转化为超稳定的喹啉基团，保持了结晶性，并在恶劣条件下赋予了特殊的化学稳定性。氟功能化使氟- cofs具有优异的疏水性，水接触角为133°。吸附研究表明，氟取代基显著调节氟虫腈的摄取，其中tpt - dhta - cof - 3f的容量比非氟类似物高193.9 mg g−1 - 2.5倍，这可归因于协同疏水和氟-氟相互作用。此外，具有3,4,5-三氟苯基片段的F-COF由于具有更高的比表面积和更大的疏水性和亲氟性而优于4-三氟甲基苯基。这些结果表明，氟化COFs是高效环境修复的有希望的平台，特别是对于持久性卤化污染物。

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Post-modified fluorine-functionalized covalent organic frameworks with excellent stability and hydrophobicity and their application in fipronil adsorption

We designed and synthesized two fluorine-functionalized covalent organic frameworks (F-COFs) TAPT-DHTA-COF-(CF₃) and TAPT-DHTA-COF-3F via post-synthetic Povarov reaction. The irreversible conversion of imine linkages into ultra-stable quinoline moieties preserved crystallinity and conferred exceptional chemical stability under harsh conditions. Fluorine functionalization conferred exceptional hydrophobicity to the F-COFs, as evidenced by water contact angles of 133°. Adsorption studies revealed that fluorine substituents significantly modulate fipronil uptake, with TAPT-DHTA-COF-3F achieving a capacity of 193.9 mg g⁻¹—2.5-fold higher than non-fluorinated analogs, which can be ascribed to synergistic hydrophobic and fluorine-fluorine interactions. In addition, the F-COF possessing 3,4,5-trifluorophenyl moiety outperforms its 4-trifluoromethylphenyl counterpart due to its higher specific surface area and greater hydrophobicity and fluorophilicity. These results establish fluorinated COFs as promising platforms for high-efficiency environmental remediation, particularly for persistent halogenated contaminants.

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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.