Precise Pore Engineering of Zirconium Metal‐Organic Cages for One‐Step Ethylene Purification from Ternary Mixtures

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Июнь 6, 2024

Abstract One‐step purification of ethylene from ternary mixtures (C 2 H , C 4 and 6 ) can greatly reduce the energy consumption separation process, but it is extremely challenging. Herein, we use crystal engineering reticular chemistry to introduce unsaturated bonds (ethynyl alkyne) into ligands, successfully design synthesized two novel Zr‐MOCs (ZrT‐1‐ethenyl ZrT‐1‐alkyne). The introduction carbon‐carbon provides abundant adsorption sites within framework while modulating pore window size. Comprehensive characterization techniques including single powder X‐ray diffraction, as well electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS) confirm that ZrT‐1‐ethenyl ZrT‐1‐alkyne possess an isostructural with ZrT‐1 ZrT‐1‐Me, respectively. Adsorption isotherms breakthrough experiments combined theoretical calculations demonstrate effectively remove trace in achieve CO . also directly purify liquid solutions. This work a benchmark for MOCs one‐step mixtures.

Язык: Английский

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Creating amphiphilic porosity in two-dimensional covalent organic frameworks via steric-hindrance-mediated precision hydrophilic-hydrophobic microphase separation

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

Опубликована: Янв. 24, 2024

Abstract Creating different pore environments within a covalent organic framework (COF) will lead to useful multicompartment structure and multiple functions, which however has been scarcely achieved. Herein we report designed synthesis of three two-dimensional COFs with amphiphilic porosity by steric-hindrance-mediated precision hydrophilic-hydrophobic microphase separation. Dictated the steric effect substituents introduced monomer, dual-pore kgm net, in all hydroxyls locate trigonal micropores while hydrophobic sidechains exclusively distribute hexagonal mesopores, have constructed form completely separated hydrophilic nanochannels. The unique channels enable formation Janus membranes via interface growth. This work realized creation two types opposite properties one COF, demonstrating feasibility introducing properties/functions into pores heteropore COFs, can be strategy develop multifunctional materials.

Язык: Английский

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Rationally Fabricating Three-Dimensional Covalent Organic Frameworks for Propyne/Propylene Separation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(50), С. 23081 - 23088

Опубликована: Дек. 9, 2022

Efficient propyne/propylene separation to obtain polymer-grade propylene is a crucial and challenging process in industrial production, but it has not yet been realized the covalent organic framework (COF) field. Addressing this challenge, we synthesize two three-dimensional COF adsorbents via [8 + 4] construction approach based on an octatopic aldehyde monomer. Upon using continuous rotation electron diffraction technique structural simulation, both COFs are successfully determined as rare flu topology. Various characterization techniques prove that exhibit high crystallinity, porosity, good stability. Attributed their interconnected micropores nonpolar pore environment, these can efficiently remove trace amounts of propyne from (1/99, 0.1/99.9, v/v) mixture high-purity (>99.99%), validated by dynamic breakthrough experiments. This work paves new avenue for highly efficient adsorbents.

Язык: Английский

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Exclusive Recognition of CO₂ from Hydrocarbons by Aluminum Formate with Hydrogen-Confined Pore Cavities

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(21), С. 11643 - 11649

Опубликована: Май 17, 2023

Exclusive capture of carbon dioxide (CO2) from hydrocarbons via adsorptive separation is an important technology in the petrochemical industry, especially for acetylene (C2H2) production. However, physicochemical similarities between CO2 and C2H2 hamper development CO2-preferential sorbents, mainly discerned C recognition with low efficiency. Here, we report that ultramicroporous material Al(HCOO)3, ALF, can exclusively hydrocarbon mixtures, including those containing CH4. ALF shows a remarkable capacity 86.2 cm3 g-1 record-high CO2/C2H2 CO2/CH4 uptake ratios. The inverse exclusive performance are validated adsorption isotherms dynamic breakthrough experiments. Notably, hydrogen-confined pore cavities appropriate dimensional size provide ideal chemistry to specifically match hydrogen bonding mechanism, all rejected. This molecular mechanism unveiled by situ Fourier-transform infrared spectroscopy, X-ray diffraction studies, simulations.

Язык: Английский

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Porous organic cages for gas separations

Materials Chemistry Frontiers, Год журнала: 2023, Номер 7(21), С. 5247 - 5262

Опубликована: Янв. 1, 2023

This review aims to provide a comprehensive overview of the recent advancements made in gas separations utilizing porous organic cages (POCs).

Язык: Английский

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Gradually Tuning the Flexibility of Two‐Dimensional Covalent Organic Frameworks via Stepwise Structural Transformation and Their Flexibility‐Dependent Properties

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Июль 27, 2023

Flexible covalent organic frameworks (COFs) are intriguing for their dynamic properties distinctive from rigid counterparts but still suffer limited accessibility. Especially, controlling flexibility of COFs is challenging and the impact different on has rarely been unveiled. This article reports stepwise adjustment two-dimensional COFs, which realized by designed synthesis COF (R-COF), semi-flexible (SF-COF), flexible (F-COF) through polymerization, linker exchange, linkage conversion with a newly developed method reduction hydrazone, respectively. Significant difference in breathing behavior self-adaptive capability three uncovered vapor response iodine capture experiments. Gas sorption experiments indicate that porosity F-COF could switch "close" state nitrogen to "open" carbon dioxide, not observed R-COF SF-COF. study only develops strategy adjust tuning linkers linkages, also provides deep insight into lays foundation development this new class porous materials.

Язык: Английский

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Single-Crystal Three-Dimensional Covalent Organic Framework Constructed from 6-Connected Triangular Prism Node

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(41), С. 22329 - 22334

Опубликована: Окт. 4, 2023

The limited structural diversity of three-dimensional covalent organic frameworks (3D COFs) greatly restricts their application exploration. Therefore, there is an urgent need to expand library molecular building blocks, such as the development highly connected (>4 reaction sites) polyhedral nodes. Herein, by precisely controlling precursor conformation, we rationally designed a new 6-connected triangular prism node derived from triphenylbenzene molecule and further used it construct novel 3D COF (3D-TMTAPB-COF) via imine condensation reaction. Surprisingly, without addition competing reagents, 3D-TMTAPB-COF crystallized directly into single crystals ∼15 μm in size was determined adopt rare 6-fold interpenetrated (Class IIIa interpenetration) acs topology. In addition, showed high SF6 adsorption capacity (60.9 cm3 g-1) good SF6/N2 selectivity (335) at 298 K 1 bar, superior those most crystalline porous materials. This work not only confirms possibility growing large-size single-crystal COFs formed with strong bonds solvothermal method absence modulators, but also reports for future construction interesting applications.

Язык: Английский

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Donor–Acceptor Covalent Organic Frameworks Films with Ultralow Band Gaps to Enhanced Third-Order Nonlinear Optical Properties

ACS Materials Letters, Год журнала: 2023, Номер 5(3), С. 694 - 703

Опубликована: Янв. 31, 2023

Covalent organic frameworks (COFs) have attracted much attention in porous materials because of their structural tunability and stability. However, the problems low transmittance large light scattering due to difficulty powder phase processing severely limited practical applications third-order nonlinear optics (NLO). Herein, we report first successful synthesis a series donor–acceptor (D–A) COFs films (thickness ∼100 nm) with uniform transparency narrow optical band gap by solvothermal solid–liquid interface methods for NLO applications. Most importantly, designed PT–PA film exhibits excellent performance, including normalized transmission value ∼2.55 at beam focus, modulation depth (As) 139%, high absorption coefficient (β) 1.83 × 106 cm GW–1 pulse energy 1 μJ, which is superior most recently reported materials. The properties are mainly attributed homogeneous extended-ordered conjugated structure films, enhance charge transfer structures thus yield behavior. This work provides an option development high-performance devices opens new path future fields.

Язык: Английский

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Integrating molecular imprinting into flexible covalent organic frameworks for selective recognition and efficient extraction of aflatoxins

Journal of Hazardous Materials, Год журнала: 2024, Номер 467, С. 133755 - 133755

Опубликована: Фев. 8, 2024

Язык: Английский

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Advances of covalent organic frameworks as the stationary phases for liquid chromatography

TrAC Trends in Analytical Chemistry, Год журнала: 2024, Номер 174, С. 117680 - 117680

Опубликована: Март 29, 2024

Язык: Английский

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