New Advances in Covalent Network Polymers via Dynamic Covalent Chemistry

Chemical Reviews, Год журнала: 2024, Номер 124(12), С. 7829 - 7906

Опубликована: Июнь 3, 2024

Covalent network polymers, as materials composed of atoms interconnected by covalent bonds in a continuous network, are known for their thermal and chemical stability. Over the past two decades, these have undergone significant transformations, gaining properties such malleability, environmental responsiveness, recyclability, crystallinity, customizable porosity, enabled development integration dynamic chemistry (DCvC). In this review, we explore innovative realm polymers focusing on recent advances achieved through application DCvC. We start examining history fundamental principles DCvC, detailing its inception core concepts noting key role reversible bond formation. Then reprocessability DCvC is thoroughly discussed, starting from milestones that marked evolution progressing to current trends applications. The influence crystallinity then reviewed, covering diversity, synthesis techniques, functionalities. concluding section, address challenges faced field speculates potential future directions.

Язык: Английский

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Pore Space Partition Synthetic Strategy in Imine-linked Multivariate Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(3), С. 1904 - 1913

Опубликована: Дек. 22, 2023

Partitioning the pores of covalent organic frameworks (COFs) is an attractive strategy for introducing microporosity and achieving new functionality, but it technically challenging to achieve. Herein, we report a simple partitioning micropores/mesopores multivariate COFs. Our approach relies on predesign synthesis multicomponent COFs through imine condensation reactions with aldehyde groups anchored in COF pores, followed by inserting additional symmetric building blocks (with C2 or C3 symmetries) as pore partition agents. This allowed tetragonal hexagonal be partitioned into two three smaller micropores, respectively. The synthesized library pore-partitioned was then applied capture iodine pollutants (i.e., I2 CH3I). rich inventory deep exploration relationships between adsorbent composition, architecture, adsorption capacity CH3I under wide-ranging conditions. Notably, one our developed (COF 3-2P) exhibited greatly enhanced dynamic performances compared its parent 3) breakthrough tests, setting benchmark COF-based adsorbents. Results present effective design toward functional tunable environments, functions, properties.

Язык: Английский

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Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid–Liquid Interface

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Март 13, 2023

Dynamic covalent chemistry (DCC) opens up a fascinating route for the construction of well-organized supramolecular architectures, starting from organic molecular cages to crystalline macromolecular frameworks (COFs). Herein, first time, we have manifested facile room-temperature DCC-directed transformation discrete imine cage-to-COF film at liquid-liquid interface. The unfolding cage leading generation intermediates, followed by their interface-assisted preorganization and subsequent growth COF film, are elucidated through detailed spectroscopic microscopic investigations. interfacial provides faster fabrication free-standing films with high porosity crystallinity, demonstrating excellent performance towards sieving solvent permeance. Thus, current study new structural interconversion between two entities diverse dimensionality employing DCC confined

Язык: Английский

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Boost of Gas Adsorption Kinetics of Covalent Organic Frameworks via Ionic Liquid Solution Process

Small, Год журнала: 2023, Номер 19(39)

Опубликована: Май 25, 2023

Abstract Adsorption, storage, and conversion of gases (e.g., carbon dioxide, hydrogen, iodine) are the three critical topics in field clean energy environmental mediation. Exploring new methods to prepare high‐performance materials improve gas adsorption is one most concerning recent years. In this work, an ionic liquid solution process (ILSP), which can greatly kinetic performance covalent organic framework (COF) for gaseous iodine, explored. Anionic COF TpPaSO 3 H modified by amino‐triazolium cation through ILSP method, successfully makes iodine (K 80% rate) (IL) AC 4 tirmTpPaSO quintuple compared with original COF. A series experimental characterization theoretical calculation results show that improvement kinetics benefited from increased weak interaction between due local charge separation skeleton caused substitution protons bulky cations ILs. This strategy has competitive help adsorption, separation, or conversion, expected expand application science.

Язык: Английский

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Solid state chemical transformation provides a fully benzoxazine-linked porous organic polymer displaying enhanced CO₂ capture and supercapacitor performance

Polymer Chemistry, Год журнала: 2023, Номер 14(20), С. 2494 - 2509

Опубликована: Янв. 1, 2023

We synthesized a fully benzoxazine (BZ)-linked POP comprising TPA and DHPT units through Sonogashira–Hagihara coupling ring opening polymerization for CO 2 capture energy storage.

Язык: Английский

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Facile Microwave-Assisted Synthesis of 2D Imine-Linked Covalent Organic Frameworks for Exceptional Iodine Capture

Precision Chemistry, Год журнала: 2023, Номер 1(4), С. 233 - 240

Опубликована: Март 17, 2023

Covalent organic frameworks (COFs) have emerged as auspicious porous adsorbents for radioiodine capture. However, their conventional solvothermal synthesis demands multiday synthetic times and anaerobic conditions, largely hampering practical use. To tackle these challenges, we present a facile microwave-assisted of 2D imine-linked COFs, Mw-TFB-BD-X, (X = -CH3 -OCH3) under air within just 1 h. The resultant COFs possessed higher crystallinity, better yields, more uniform morphology than counterparts. Remarkably, Mw-TFB-BD-CH3 Mw-TFB-BD-OCH3 exhibited exceptional iodine adsorption capacities 7.83 g g-1 7.05 g-1, respectively, placing them among the best-performing COF static vapor Moreover, can be reused 5 with no apparent loss in capacity. exceptionally high excellent reusability were mainly attributed to spherical enhanced chemical stability due in-built electron-donating groups, despite low surface areas. This work establishes benchmark developing advanced that combine fast kinetics, capacity, reusability, rapid synthesis, set appealing features remain challenging merge so far.

Язык: Английский

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Counteranion-mediated efficient iodine capture in a hexacationic imidazolium organic cage enabled by multiple non-covalent interactions

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Сен. 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.

Язык: Английский

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Ultralight crystalline hybrid composite material for highly efficient sequestration of radioiodine

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 10, 2024

Abstract Considering the importance of sustainable nuclear energy, effective management radioactive waste, such as sequestration radioiodine has inflicted a significant research attention in recent years. Despite fact that materials have been reported for adsorption iodine, development adsorbent with significantly improved segregation properties widespread practical applications still remain exceedingly difficult due to lack proper design strategies. Herein, utilizing unique hybridization synthetic strategy, composite crystalline aerogel material fabricated by covalent stepping an amino-functionalized stable cationic discrete metal-organic polyhedra dual-pore containing imine-functionalized organic framework. The ultralight hybrid exhibits large surface area hierarchical macro-micro porosity and multifunctional binding sites, which collectively interact iodine. developed nano-adsorbent demonstrate ultrahigh vapor aqueous-phase iodine capacities 9.98 g.g −1 4.74 , respectively, static conditions fast kinetics, high retention efficiency, reusability recovery.

Язык: Английский

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Chiral Memory in Dynamic Transformation from Porous Organic Cages to Covalent Organic Frameworks for Enantiorecognition Analysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7594 - 7604

Опубликована: Март 11, 2024

The preservation of chirality during a transformation process, known as the "chiral memory" effect, has garnered significant attention across multiple research disciplines. Here, we first report retention original chiral structure dynamic covalent chemistry (DCC)-induced structural from porous organic cages into frameworks (COFs). A total six two-dimensional COFs constructed by entirely achiral building blocks were obtained through DCC-induced substitution linkers in homochiral cage (CC3-R or -S) using amine monomers. Homochirality these resulted construction 3-fold-symmetric benzene-1,3,5-methanimine cores with propeller-like configuration one single-handedness throughout cage-to-COF transformation. can be further utilized fluorescence sensors stationary phases for gas chromatography high enantioselectivity. present study thus highlighted great potential to expand scope functional materials via crystal-to-crystal memory effect.

Язык: Английский

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Covalent organic polymers for efficient removal of iodine from gas- and liquid-phase environments

Chemical Engineering Journal, Год журнала: 2024, Номер 484, С. 149739 - 149739

Опубликована: Фев. 16, 2024

Язык: Английский

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