Recent progress in iodine capture by macrocycles and cages

Zhou, Weinan; Lavendomme, Roy; Zhang, Dawei

doi:10.1039/d3cc05337g

Cited by 13 publications

(4 citation statements)

References 89 publications

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“…Efficiently capturing radioactive iodine is crucial for ensuring the safe and sustainable utilization of nuclear energy. Certain organic cages featuring nitrogen-rich functional groups have shown exceptional abilities for adsorbing iodine. − However, the densely packed structure of normal cages in their solid form hinders their ability to interact with iodine during the adsorption process. Additionally, their high solubility in aqueous solutions poses challenges for recycling.…”

Section: Synthesis and Applications Of Cage-based Cofsmentioning

confidence: 99%

Synthesis and Applications of Cage-Based Covalent Organic Frameworks

Dutta,

Hernández García,

Mishra

et al. 2024

Crystal Growth & Design

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Due to their unique structural characteristics, molecular cages have become pivotal components in supramolecular chemistry and materials science. These cages possess the remarkable ability to encapsulate guest molecules and metal nanoparticles within their cavities, fostering intriguing host−guest interactions and demonstrating significant potential across various domains, including molecular recognition, drug delivery, catalysis, and material synthesis. Integrating these molecular cages with highly porous crystalline covalent organic frameworks (COFs) constitutes a strategic avenue for enhancing both porosity and functional sites. This transition from molecular cages to COF frameworks involves the precise orchestration of individual molecules into extended, covalently bonded structures with welldefined frameworks and porosity. This unlocks novel pathways for materials design and applications, significantly enriching the landscape of materials science. This review comprehensively summarizes the synthetic strategies employed in fabricating cage-based COFs, explores their diverse applications, and provides insights into the future prospects and growth of this rapidly evolving field.

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Section: Synthesis and Applications Of Cage-based Cofsmentioning

confidence: 99%

Synthesis and Applications of Cage-Based Covalent Organic Frameworks

Dutta,

Hernández García,

Mishra

et al. 2024

Crystal Growth & Design

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“…Incorporating supramolecular macrocycles can endow the material with remarkable functions. − Typically, electron-rich macrocycles, such as pillararene, ,,− calix[4]arenes, calix[4]resorcinarene, calix[4]pyrrole, − and cucurbit[ n ]urils, , are employed to construct I 2 or CH 3 I capture materials. Among them, pillar[ n ]arenes (P[ n ]A) are a macrocyclic host with rigid pillars and π-electron-rich external walls/cavities.…”

Section: Introductionmentioning

confidence: 99%

Linking Nitrogen-Rich Pillar[5]arene to Hyper-Cross-Linked Polymers for Efficient and Simultaneous Capture of Iodine and Methyl Iodide

Zhang,

Yue,

Jiang

et al. 2024

ACS Appl. Polym. Mater.

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The simultaneous capture of radioactive molecular iodine (I 2 ) and methyl iodide (CH 3 I) coexisting in the exhaust stream of nuclear power plants has become an urgent and challenging task. However, there are a few adsorbents that can be used to achieve this goal. Herein, three nitrogen-rich pillar[5]arene-based hyper-cross-linked polymers are presented. Among these polymers, P[5]A-TPTA12, which was constructed with deca-(diethylaminoethoxy)pillar[5]arene and 2, 4, 6-tris(4-(bromomethyl)phenyl)-1, 3, 5-triazine, exhibited excellent uptake capacities for iodine gas (4.83 g g −1 ) and methyl iodine (1.08 g g −1 ) under static sorption conditions. A great deal of effective and diverse desorption sites, including nucleophilic N sites, aromatic rings, and oxygen atoms, were responsible for the excellent adsorption capacity. The work presented not only an important method for the removal of radioactive contaminants but also a remarkable employment of macrocyclebased materials in environmental remediation.

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“…The research on iodine capture centers on developing high-performance adsorbent materials. − Various adsorbents, such as silver-based zeolites, activated carbons, metal–organic frameworks (MOFs), ,− covalent organic frameworks (COFs), − and porous organic polymers (POPs), − have been extensively studied for their potential use in iodine removal. In addition to these porous materials, porous organic cages (POCs) have recently been utilized as alternative adsorbents to capture iodine. ,− Compared to the extended polymeric materials, like MOFs, COFs, or POPs, that only have external pores, POCs comprise discrete organic cage molecules with intrinsic cavities and accessible windows. These accessible internal voids can be tailored differently in size, shape, and functionalities, allowing POCs to selectively accommodate specific guest molecules or ions. , POCs like CC3, BTPOC, OMC3, BPy-CAGE, BPPOC, SUPE-py-Imine-Cage, and imidazolium cages have shown promising results for iodine capture.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Triazole-Linked Porous Cage Polymers: Modulating Cage Size for Tailored Iodine Adsorption

Begar,

Erdogmus,

Gecalp

et al. 2024

ACS Appl. Polym. Mater.

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We present the synthesis of two triazole-linked porous cage polymers (pCAGEs) using two D 3h symmetric shapepersistent organic cages of different sizes as monomers. We observed that expanding the size of the cage monomer resulted in an improved surface area, pore volume, and iodine vapor uptake capacity of up to 4.02 g g −1 at 75 °C under ambient pressure. Also, embedding molecular organic cages into pCAGEs boosted their iodine adsorption performances compared to their discrete molecular counterparts, model compounds (mCAGEs), due to their open pore channels, enabling the efficient diffusion of iodine into the binding sites. The pCAGEs showed promising iodine adsorption efficiencies from a concentrated KI/I 2 aqueous solution with a high iodine uptake capacity of up to 3.35 g g −1 . The iodine uptake capacities of pCAGEs differ in vapor and aqueous solutions, which suggests that tuning the cage size allows us not only to control the textural properties of pCAGEs but also to tailor their iodine adsorption performances in vapor and water. Iodine adsorption mechanisms of pCAGEs were investigated using ex situ structural characterization techniques, revealing strong interactions of adsorbed iodine species with nitrogen-rich groups and phenyl rings of the pCAGEs. Notably, pCAGEs demonstrated remarkable regeneration and reusability, maintaining 86% of their initial adsorption capacities over five adsorption/desorption cycles, highlighting their potential for practical applications. These findings contribute to a fundamental understanding of the structure− property relationship for cage-based polymeric materials and provide insights into the development of high-performance adsorbents for iodine capture.

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Recent progress in iodine capture by macrocycles and cages

Abstract: Advances of macrocycle and cage-based materials for iodine capture, with an emphasis on the structure of hosts, complexation mechanism and adsorption efficiency, have been summarized.

Cited by 13 publications

References 89 publications

Synthesis and Applications of Cage-Based Covalent Organic Frameworks

Synthesis and Applications of Cage-Based Covalent Organic Frameworks

Linking Nitrogen-Rich Pillar[5]arene to Hyper-Cross-Linked Polymers for Efficient and Simultaneous Capture of Iodine and Methyl Iodide

Synthesis of Triazole-Linked Porous Cage Polymers: Modulating Cage Size for Tailored Iodine Adsorption

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