Designing Organic–Inorganic Hybrid Materials to Construct a Complementary Interface with Versatility for Li–S Batteries

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 3, 2024

Abstract Polysulfides shuttle and lithium dendrites growth greatly restricts the practical application of lithium–sulfur batteries (LSBs). A rational designed separator combined polysulfide catalyst regulator can achieve effect killing two birds with one stone. Herein, organic–inorganic hybrid materials are to construct a complementary interface for LSBs. Specially, kinds covalent organic frameworks (COF) different pore size in situ grown on MXene surface by forming Ti–N bond. The high electronic conductivity abundant functional groups allow it work as effectively accelerate polysulfides conversion, while COF be used an ion calibrator guide homogeneous deposition. As expected, MXene@COF (MCOF) integrated realizes advantages that enable Li||Li symmetric cell surprisingly stable plating/stripping process up 4750 h at 10 mA cm −2 . Furthermore, assembled LSBs exhibit capacities 584/563 mAh g −1 3 C low‐capacity decay rates 0.042%/0.048% per cycle after 1000 cycles 1 C. This proposes strategy based composites layer, which is great significance construction high‐performance

Language: Английский

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Construction and Band Gap-Regulation of Ordered Macro–Microporous Single Crystals of an Amine-Linked Covalent Organic Framework

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Heterogeneity engineering provides an effective route to manipulate the chemical and physical properties of covalent organic frameworks (COFs) but is still under development for their single-crystal form. Here, we report strategy based on a combination template-assisted modulated synthesis with one-pot crystallization-reduction method directly construct ordered macro-microporous single crystals amine-linked three-dimensional (3D) COF (OM-COF-300-SR). In this strategy, colloidal crystal-templating not only assists formation macropores also greatly facilitates in situ conversion linkages (from imine amine) COF-300 crystals. The as-synthesized OM-COF-300-SR120 exhibits reversible symmetry change from tetragonal I41/a monoclinic I2/c space group after activation, which was observed previously. On other hand, allows flexible control over degree amination 0 100%, as determined by X-ray photoelectron spectroscopy (XPS) analysis) regulate band gap 2.57 2.81 eV) optimization photocatalytic activity. high embedded render superior activity (with reaction rate constant 0.9572 min-1) its nonmacroporous counterpart (NM-COF-300-SR120, 0.2303 degradation rhodamine B. addition, significant contribution confront mass transfer resistance confirmed much higher catalytic Au/OM-COF-300-SR120 parameter 7.96 × 103 s-1 mol-1) compared Au/NM-COF-300-SR120 (1.43 model reduction 4-nitrophenol NaBH4.

Language: Английский

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Developing a One‐Pot Strategy to Synthesize Metal–Covalent Organic Frameworks as Catalysts for Polysulfide Conversion and Ion Calibrators for Lithium Deposition

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Abstract Introducing metals into covalent organic frameworks (COFs) to synthesize metal‐COFs (MCOFs) presents novel opportunities for designing highly efficient catalysts address the sluggish conversion of polysulfides and developing effective ion calibrators mitigate uncontrolled lithium dendrite growth in lithium–sulfur batteries (LSBs). Herein, a facile one‐pot strategy is proposed integrate Zn single atoms COF framework through coordination with N O atoms. Comprehensive characterizations microstructure, morphology, chemical environment provide convincing evidence that exists Zn‐COF as +2 state. Leveraging synergistic advantages high content (12.43%) an ordered porous structure, demonstrates excellent catalytic activity polysulfide conversion, effectively suppressing shuttle effect enhancing reaction kinetics. Additionally, structure promotes uniform lithium‐ion flow, facilitating homogeneous deposition. Consequently, comprehensive electrochemical performance LSBs significantly improved under both conventional high‐sulfur‐loading conditions. This work simple scalable integrating COFs, thereby introducing robust sites structures LSBs. It offers valuable insights advancing catalysis inhibition strategies.

Language: Английский

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Regulating the Azo‐Functionalization of Covalent Organic Frameworks for Photo‐Modulated Adsorption and Sensing of Aniline

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Abstract Photoresponsive materials have garnered considerable attention, particularly azo‐functionalized covalent organic frameworks (COFs), due to their unique ability undergo cis/trans isomerization under UV/visible light irradiation, making them highly promising in the field of adsorption. In this work, innovative post‐synthetic modification (PSM) approach is developed introduce azobenzene groups, resulting construction three COFs with varying degrees azo‐functionalization (ThTFB‐nN = N, n 1, 2, 3). It found that ThTFB‐nN N exhibits reversible alternating irradiation 365 and 450 nm light, degree azo content within framework, as well trans ‐ cis isomerization, can significantly influence material's properties. Notably, ‐ThTFB‐3N demonstrates highest adsorption capacity for aniline at 303.3 mg·g −1 , representing a nearly tenfold enhancement compared (30.7 ). Additionally, ThTFB‐3N shows excellent fluorescence detection capability aniline, achieving limit 22 ppb. To investigate underlying mechanisms detection, density functional theory (DFT) calculations are conducted. conclusion, work introduces novel PSM strategy incorporating photoresponsive units, leading multifunctional material substantial potential detection.

Language: Английский

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Donor–Acceptor Type Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(14)

Published: April 1, 2025

Abstract Covalent organic frameworks (COFs) as a new type of crystalline porous material with tunable structures are widely used in the field photocatalytic hydrogen evolution (PHE) due to their large specific surface area and abundant active sites. However, electron‐hole recombination during reaction process hinders progress reaction. Donor–acceptor (D–A) COFs can effectively promote charge carrier transport enhance light harvesting capability by introducing D units A into framework. The D–A have unique advantages PHE. This concept review concentrates on recent developments for PHE necessary modules constructing COFs. Moreover, it summarizes challenges faced development directions future.

Language: Английский

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Structure-Induced Selectivity of Hydroxylated Covalent Organic Framework Nanofibers for Advanced Sensing Applications: An Experimental and Density Functional Theory Study

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: April 26, 2025

This study reports on the rational design of hydroxyl-functionalized covalent organic framework nanofibers (HO-COFs: PyTA-2,3-NA(OH)2 and PyTA-2,6-NA(OH)2) by a scalable solvothermal method. The resulting HO-COF is more hydrophilic than PyTA-2,6-NA(OH)2 HO-COF, which can effectively enhance sensitivity sensor toward basic ethylenediamine (EDA). fabricated nanofiber-based quartz crystal microbalance exhibits rapid sensing response distinguished selectivity EDA vapor, arising from strong hydrogen bonding interactions with NH2 groups EDA, as investigated wide variety chemical analysis techniques density functional theory calculations. presence exposed neighboring hydroxyl that face same direction in present exhibited efficient interactions. nanofiber 1.6 times higher to 100 ppm (ppm) opposite directions, low limit detection 2.9 ppm. structure has abundant active facing direction, making them favorable sites for binding molecules through bond color changed after exposure colorimetric assessment naked-eye detection. These exhibit remarkable other interfering vapors show high stability only 6.4% drop 6 months. adsorption follows pseudo-first-order kinetic model, an rate about 8.0 faster nanofibers. findings this highlight potential use COFs, particularly those close groups, effective materials selective harmful EDA.

Language: Английский

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Amino-Yne Click Polymerized β-Ketoenamine-Based Covalent Organic Frameworks for Enhanced Photocatalytic Performance

ACS Materials Letters, Journal Year: 2024, Volume and Issue: unknown, P. 5292 - 5299

Published: Nov. 4, 2024

Constructing β-ketoenamine-linked covalent organic frameworks (COFs) for photocatalysis is highly attractive but remains challenging due to limited reaction types and monomer availability. Herein, we highlight the critical role of amino-yne click polymerization in overcoming these challenges enabling successful synthesis a novel COF, named En-COF-P. This new approach not only simplifies process also significantly expands chemical linkages available COF construction. The resulting En-COF-P exhibits an enhanced visible light absorption range, facilitating improved charge generation separation. These properties translate into remarkable photocatalytic performance, particularly blue-light-driven selective oxidation sulfides, where achieves up 99% conversion selectivity. Remarkably, En-COF-P's efficiency eight times higher than that traditional imine-linked COFs. work underscores potential advances strategy design efficient photocatalysts.

Language: Английский

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Machine-Learning Discovered Crystallization Model for Two-Dimensional Covalent Organic Frameworks: Towards Precise Control of the Crystal Quality

Published: March 5, 2024

The rational molecular design and experimental condition optimizations for two-dimensional covalent organic frameworks (2D COFs) call a crystallization model capable of capturing time size scales. However, accurately describing their process remains significant challenge due to the presence non-classical pathways. Here, we demon-strate implementation machine-learning approach, overcoming difficulties associ-ated with bottom-up derivation. resulting model, referred as NEgen1, establishes correlations among induction time, nucleation rate, growth material parameters, common solution synthesis conditions 2D COFs that belong nucleation-elongation category. NEgen1 represents emergence practical models COFs, enabling direct calculation processes in both times sizes. results elucidate detailed competition between dynam-ics solution, which has been inappropriately apprehended via classical, empirical assumptions invalid COFs. Importantly, demonstrate potential application optimizing conditions, predominantly relied on knowledge date. identification superior those routinely used experimentally reveals promising strategy gradually increasing monomer addition speed growing large COF crystals while maintaining reasonable time. These highlight systematically improving crystal quality wider applications.

Language: Английский

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Machine-Learning Discovered Crystallization Model for Two Dimensional Covalent Organic Frameworks: Towards Precise Control of the Crystal Quality

Published: April 8, 2024

The rational molecular design and experimental condition optimizations for two-dimensional co-valent organic frameworks (2D COFs) call a crystallization model capable of capturing exper-imental time size scales. However, accurately describing their process remains significant challenge due to the presence non-classical pathways. Here, we demonstrate implementation machine-learning approach, overcoming difficulties associated with bot-tom-up derivation. resulting model, referred as NEgen1, establishes correlations among induction time, nucleation rate, growth material parameters, common solu-tion synthesis conditions 2D COFs that belong nucleation-elongation category. NEg-en1 represents emergence practical models COFs, enabling direct calculation processes in both times sizes. results elu-cidate detailed competition between dynamics solution, which has been inappropriately apprehended via classical, empirical assumptions invalid COFs. Importantly, potential application NEgen1 opti-mizing conditions, predominantly relied on knowledge date. identification superior those routinely used experimentally reveals promis-ing strategy gradually increasing monomer addition speed growing large COF crystals while maintaining reasonable time. These highlight systemati-cally improving crystal quality wider applications.

Language: Английский

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Toward Pore Size-Selective Photoredox Catalysis Using Bifunctional Microporous 2D Triazine-Based Covalent Organic Frameworks

ACS Omega, Journal Year: 2024, Volume and Issue: 9(50), P. 49249 - 49258

Published: Dec. 6, 2024

The design and synthesis of photoactive metal-free 2D materials for selective heterogeneous photoredox catalysis continue to be challenging due issues related nonrecyclability, limited photo- chemical stability. Herein, we report the photocatalytic properties a triazine-based porous COF,

Language: Английский

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