Counteranion-mediated efficient iodine capture in a hexacationic imidazolium organic cage enabled by multiple non-covalent interactions DOI Creative Commons
Jian Yang,

Shao‐Jun Hu,

Li‐Xuan Cai

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Sept. 28, 2023

Developing efficient adsorbents to capture radioactive iodine produced from nuclear wastes is highly desired. Here we report the facial synthesis of a hexacationic imidazolium organic cage and its adsorption properties. Crucial role counteranions has been disclosed for with this cage, where distinct behaviors were observed when different used. Mechanistic investigations, especially X-ray crystallographic analysis iodine-loaded sample, allowed direct visualization binding modes at molecular level. A network multiple non-covalent interactions including hydrogen bonds, halogen anion···π interactions, electrostatic interaction between polyiodides skeleton are found responsible high performance. Our results may provide an alternative strategy design adsorbents.

Language: Английский

Ionic Functionalization of Multivariate Covalent Organic Frameworks to Achieve an Exceptionally High Iodine‐Capture Capacity DOI
Yaqiang Xie, Tingting Pan, Qiong Lei

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(41), P. 22432 - 22440

Published: Aug. 24, 2021

Abstract Adsorption‐based iodine (I 2 ) capture has great potential for the treatment of radioactive nuclear waste. In this study, we apply a “multivariate” synthetic strategy to construct ionic covalent organic frameworks (iCOFs) with large surface area, high pore volume, and abundant binding sites I capture. The optimized material iCOF‐AB‐50 exhibits static uptake capacity 10.21 g −1 at 75 °C dynamic 2.79 ≈400 ppm 25 °C, far exceeding performances previously reported adsorbents under similar conditions. also fast adsorption kinetics, good moisture tolerance, full reusability. promoting effect groups on been elucidated by experimentally identifying species adsorbed different calculating their energies. This work demonstrates essential role balancing textural properties adsorbent in achieving performance.

Language: Английский

Citations

262
Efficient and simultaneous capture of iodine and methyl iodide achieved by a covalent organic framework DOI Creative Commons
Yaqiang Xie, Tingting Pan, Qiong Lei

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 24, 2022

Radioactive molecular iodine (I2) and organic iodides, mainly methyl iodide (CH3I), coexist in the off-gas stream of nuclear power plants at low concentrations, whereas few adsorbents can effectively adsorb low-concentration I2 CH3I simultaneously. Here we demonstrate that adsorption occur on various adsorptive sites be promoted through intermolecular interactions. The capacity is positively correlated with content strong binding but unrelated to textural properties adsorbent. These insights allow us design a covalent framework simultaneously capture concentrations. developed material, COF-TAPT, combines high crystallinity, large surface area, abundant nucleophilic groups exhibits record-high static (1.53 g·g-1 25 °C). In dynamic mixed-gas 150 ppm 50 CH3I, COF-TAPT presents an excellent total (1.51 g·g-1), surpassing benchmark adsorbents. This work deepens understanding I2/CH3I mechanisms, providing guidance for development novel related applications.

Language: Английский

Citations

242
Chemically Stable Guanidinium Covalent Organic Framework for the Efficient Capture of Low-Concentration Iodine at High Temperatures DOI
Zhiyuan Zhang, Xinglong Dong, Jun Yin

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(15), P. 6821 - 6829

Published: April 5, 2022

The capture of radioactive I2 vapor from nuclear waste under industrial operating conditions remains a challenging task, as the practical high temperature (≥150 °C) and low concentration (∼150 ppmv) are unfavorable for adsorption. We report novel guanidinium-based covalent organic framework (COF), termed TGDM, which can efficiently conditions. At 150 °C ppmv I2, TGDM exhibits an uptake ∼30 wt %, is significantly higher than that silver-based adsorbents such Ag@MOR (17 %) currently used in fuel reprocessing industry. Characterization theoretical calculations indicate among multiple types adsorption sites only ionic bond to through strong Coulomb interactions harsh abundant groups account its superior performance compared various benchmark adsorbents. In addition, exceptionally chemical thermal stabilities fully meet requirements (high-temperature, humid, acidic environment) differentiate it other COFs. Furthermore, has excellent recyclability cost, unavailable current These advantages make promising candidate capturing during reprocessing. This strategy incorporating chemically stable guanidine moieties COF would stimulate development new related applications.

Language: Английский

Citations

174
Transformation of Porous Organic Cages and Covalent Organic Frameworks with Efficient Iodine Vapor Capture Performance DOI
Chao Liu, Yucheng Jin,

Zonghua Yu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(27), P. 12390 - 12399

Published: June 29, 2022

The reaction of 5,5′-([2,2′-bipyridine]-5,5′-diyl)diisophthalaldehyde (BPDDP) with cyclohexanediamine and [benzidine (BZ)/[2,2′-bipyridine]-5,5′-diamine (BPDA)], respectively, affords a nitrogen-rich porous organic cage BPPOC two two-dimensional (2D) covalent frameworks (COFs), USTB-1 USTB-2 (USTB = University Science Technology Beijing), under suitable conditions. Interestingly, single-crystal X-ray diffraction structure is able to successfully transform into (newly converted COFs denoted as USTB-1c USTB-2c, respectively) upon exchange the imine unit in by BZ BPDA. Such transformation also enables isolation analogous (USTB-3c USTB-4c) on basis an isostructural cage, BTPOC, which derived from 5,5′-([2,2′-bithiophene]-4,4′-diyl)diisophthalaldehyde (BTDDP) cyclohexanediamine. However, conventional solvothermal between BTDDP BPDA leads impure phase USTB-4 containing incompletely aldehyde groups due limited solubility building block. newly prepared have been characterized nuclear magnetic resonance spectroscopy, Fourier infrared scanning electron microscopy, transmission microscopy. In particular, absorb iodine vapor uptake 5.64 g g–1, breaking cage's (POC's) record value 3.78 g–1. Nevertheless, cage-derived exhibit improved adsorption capability comparison directly synthesized counterparts, highest 5.80 g–1 for USTB-1c. mechanism investigation unveils superiority nitrogen atoms sulfur POCs capture assistance definite crystal structures. This, combination porosity, synergistically influences capacity COFs.

Language: Английский

Citations

157
Advanced porous adsorbents for radionuclides elimination DOI
Mengjie Hao, Yanfang Liu,

Weijin Wu

et al.

EnergyChem, Journal Year: 2023, Volume and Issue: 5(4), P. 100101 - 100101

Published: Feb. 14, 2023

Language: Английский

Citations

156
Reversible Iodine Capture by Nonporous Adaptive Crystals of a Bipyridine Cage DOI
Dan Luo,

Yanlei He,

Jinya Tian

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 113 - 117

Published: Dec. 28, 2021

The ability to capture radioactive iodine species is crucial for nuclear accident preparedness and waste treatment; however, it remains a challenge. Here we report new readily obtainable nitrogen-rich nonporous cage (BPy-Cage) based on bipyridine building blocks that supports capture. This able not only volatile in vapor form but also dissolved various organic solvents or aqueous media with an uptake capacity of up 3.23 g g-1. within the (I2@BPy-Cage) can be released quickly upon immersing bound solid DMF, allowing control over acylation reactions. solids reported here could reused several times without substantial loss their performance. effectiveness present system ascribed its support strong iodine-bipyridine nitrogen lone pair interactions.

Language: Английский

Citations

141
Tetrathiafulvalene-based covalent organic frameworks for ultrahigh iodine capture DOI Creative Commons

Jianhong Chang,

Hui Li,

Jie Zhao

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(24), P. 8452 - 8457

Published: Jan. 1, 2021

The synergistic effect of physical and chemical adsorption iodine in tetrathiafulvalene-based covalent organic frameworks (COFs) has been explored. capacity these materials is higher than other reported so far.

Language: Английский

Citations

139
Adsorption-based capture of iodine and organic iodides: status and challenges DOI Creative Commons
Tingting Pan, Kaijie Yang, Xinglong Dong

et al.

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(11), P. 5460 - 5475

Published: Jan. 1, 2023

This review discusses the current status and challenges in development of novel iodine capture adsorbents, focusing on adsorption mechanisms evaluation methods.

Language: Английский

Citations

136
Ordered Macro–Microporous Single Crystals of Covalent Organic Frameworks with Efficient Sorption of Iodine DOI
Tong Liu,

Yi Zhao,

Min Song

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2544 - 2552

Published: Jan. 20, 2023

Fashioning microporous covalent organic frameworks (COFs) into single crystals with ordered macropores allows for an effective reduction of the mass transfer resistance and maximum preservation their intrinsic properties but remains unexplored. Here, we report first synthesis three-dimensional (3D) macroporous imine-linked 3D COFs (COF-300 COF-303) via a template-assisted modulated strategy. In this strategy, crystallized within sacrificial colloidal crystal template, assembled from monodisperse polystyrene microspheres, underwent aniline-modulated amorphous-to-crystalline transformation to form large interconnected macropores. The effects introduced structure on sorption performances COF-300 were further probed by iodine. Our results indicate that iodine adsorption occurred in micropores not Accordingly, capacity COF was governed micropore accessibility. relatively long diffusion path non-macroporous resulted limited accessibility (48.4%) thus low (1.48 g·g-1). introduction can greatly shorten render all fully accessible (3.15 g·g-1) coincides well theoretical one.

Language: Английский

Citations

123
Structure–performance correlation guided applications of covalent organic frameworks DOI
Hou Wang, Yi Yang, Xingzhong Yuan

et al.

Materials Today, Journal Year: 2022, Volume and Issue: 53, P. 106 - 133

Published: Feb. 25, 2022

Language: Английский

Citations

113