Vinylene‐linked Donor‐π‐Acceptor Metal‐Covalent Organic Framework for Enhanced Photocatalytic CO2 Reduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Sept. 3, 2024

Abstract Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal‐covalent organic framework (MCOF) based photocatalyst. However, robust achieving both simultaneously has yet to be challenging despite ongoing efforts. Here we develop a fully π‐conjugated vinylene‐linked multivariate donor‐π‐acceptor MCOF (D‐π‐A, termed UJN‐1) by integrating benzyl cyanides linker with multiple functional electron‐rich triphenylamine electron‐deficient copper‐cyclic trinuclear units (Cu‐CTUs) moieties, featuring strong intramolecular force, extended conjugation degree skeleton, abundant active sites. The incorporation Cu‐CTUs acceptor electron‐withdrawing ability concomitantly giant can efficiently accelerate photogenerated electrons transfer from Cu‐CTUs, revealing experiments theoretical calculations. Benefiting synergistically effect D‐π‐A configuration vinylene linkage, highly‐efficient spatial is achieved. Consequently, UJN‐1 exhibits an excellent CO formation rate 114.8 μmol g −1 in 4 h without any co‐catalysts or sacrificial reagents under visible light, outperforming those analogous MCOFs imine‐linked (UJN‐2, 28.9 ) COF Cu‐CTU sites (UJN‐3, 50.0 ), emphasizing role designing novel COFs‐based

Language: Английский

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Rational design of Bacteria-Targeted and Photo-Responsive MOF gel with antibacterial and anti-inflammatory function for infected wound healing

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 493, P. 152760 - 152760

Published: June 1, 2024

Language: Английский

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Covalent Metal–Organic Frameworks: Fusion of Covalent Organic Frameworks and Metal–Organic Frameworks

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

ConspectusMetal-organic frameworks (MOFs) and covalent organic (COFs), as emerging porous crystalline materials, have attracted remarkable attention in chemistry, physics, materials science. MOFs are constructed by metal clusters (or ions) linkers through coordination bonds, while COFs prepared pure building blocks via bonds. Because of the nature linkages, their own shortcomings. Typically, relatively weak bond strengths bonds lead to poor chemical stability MOFs, which limits practical implementations. On other hand, due strong exhibit rather higher under harsh conditions, compared MOFs. However, lack open sites restricts functionalization application. Therefore, it is hypothesized that "cream-skimming" would address these drawbacks produce a new class material, namely, metal-organic (CMOFs), with unprecedented structural complexity advanced functionality. The CMOFs reveal synthetic approach for preparation reticular materials. Specifically, ions reacted chelating ligands assemble complexes or functional reactive (e.g., -CHO, -NH2), can be further connected form networked structures dynamic chemistry (DCC). isolated complex cluster precursors show enhanced prevents decomposition rearrangements during self-assembly process CMOFs. Since topology preassembled nodes well-defined, structure readily predicted upon directed networking Unaccessible from unstable highly ion/clusters traditional conditions DCC approach. Moreover, synergize advantages COFs, containing active ensuring various interesting properties, linkages allow high even conditions. In past few years, our group has specifically focused on development general strategies coinage (Cu, Ag, Au)-based cyclic trinuclear units (CTUs) DCC. CTUs trigonal planar functionalized sites, such -NH2 react afford Notably, also features properties including metallophilic attraction, π-acidity/basicity, luminescence, redox activity catalytic activity, incorporated into we envision promising platforms not only novel but potential applications many research fields gas absorption/separation, sensing, full-color display, catalysis, energy, biological applications. this Account, summarize recent studies CMOFs, starting linkage topological design, transformation, morphological control, fields. We discuss future opportunities challenges rapidly developed field hope Account may promote scientific discoveries CMOF-based technologies future.

Language: Английский

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Covalent copper-organic frameworks with light-activable catalytic centers as smart artificial enzymes for highly sensitive and wide-range biocatalytic diagnosis

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 490, P. 151881 - 151881

Published: May 3, 2024

Language: Английский

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Dual Redox‐active Covalent Organic Framework‐based Memristors for Highly‐efficient Neuromorphic Computing

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 6, 2024

Abstract Organic memristors based on covalent organic frameworks (COFs) exhibit significant potential for future neuromorphic computing applications. The preparation of high‐quality COF nanosheets through appropriate structural design and building block selection is critical the enhancement memristor performance. In this study, a novel room‐temperature single‐phase method was used to synthesize Ta−Cu 3 COF, which contains two redox‐active units: trinuclear copper triphenylamine. resultant were dispersed acid‐assisted exfoliation subsequently spin‐coated fabricate film an indium tin oxide (ITO) substrate. synergistic effect dual centers in film, combined with its distinct crystallinity, significantly reduces redox energy barrier, enabling efficient modulation 128 non‐volatile conductive states Al/Ta−Cu COF/ITO memristor. Utilizing convolutional neural network (CNN) these conductance states, image recognition ten representative campus landmarks successfully executed, achieving high accuracy 95.13 % after 25 training epochs. Compared devices binary exhibits 45.56 improvement enhances efficiency computing.

Language: Английский

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Light-activated bifunctional nanozymes based on three-component covalent organic frameworks for colorimetric and ratiometric fluorescence dual-mode detection of alkaline phosphatase

Sensors and Actuators B Chemical, Journal Year: 2024, Volume and Issue: 422, P. 136593 - 136593

Published: Sept. 5, 2024

Language: Английский

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A Hierarchical Metal–Organic Framework Intensifying ROS Catalytic Activity and Bacterial Entrapment for Engineering Self‐Antimicrobial Mask

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

Leveraging functional materials to develop advanced personal protective equipment is of significant importance for cutting off the propagation infectious diseases, yet faces ongoing challenges owing unsatisfied antimicrobial efficiency. Herein a hierarchically porous cerium metal-organic framework (Ce-MOF) boosting performance by intensifying catalytic reactive oxygen species (ROS) generation and bacterial entrapment simultaneously reported. This Ce-MOF presents dendritic surface topography hierarchical pore channels where Lewis acid Ce sites are dispersedly anchored. Attributing this sophisticated nanoarchitecture rendering highly accessible, it shows ca. 1800-fold activity enhancement conversion atmospheric toxic ROS compared traditional CeO

Language: Английский

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Cobalt-Cluster-Triggered Exfoliation for Ultrathin Metal–Covalent Organic Framework Nanosheets

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 26, 2025

Metal–covalent organic frameworks (MCOFs), an emerging type of porous material, have the combined advantages metal–organic (MOFs) and covalent (COFs). Of particular interest are MCOF nanosheets with two-dimensional morphology, whose fully exposed active sites quasi-molecular size expected to exhibit maximum functionality for a wide range applications. However, due their strong interlayer coupling potential structural damage during synthesis process, preparation has rarely been reported. Here, we demonstrate cobalt-cluster-triggered chemical exfoliation strategy directly prepare ultrathin from bulk COFs. By reaction cobalt carbonyl alkynyl-based COFs at room temperature, constructed under mild conditions. The mechanism direct growth includes formation stable clusters within COF skeletons, which alters alkynyl bonds related dihedral angle disrupts interactions. Consequently, converted into nanosheets, yield 40%, average lateral 0.8 μm, thickness 1.6 nm. This lays foundation application by treating carbonyl.

Language: Английский

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Redox‐Active Metal‐Covalent Organic Frameworks for Dendrite‐Free Lithium Metal Batteries

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

Published: Feb. 25, 2025

Abstract Lithium (Li) metal has gained attention as an anode material for lithium‐metal batteries (LMBs) owing to its low electrochemical potential, high specific capacity, and density. However, the accumulation of Li dendrites unstable solid electrolyte interphases, caused by sluggish + migration uneven deposition, limit practical LMB applications. This study presents first report on redox‐active metal–covalent organic frameworks (MCOFs) with dual‐active centers functional separators LMBs. These MCOFs facilitate homogeneous nucleation accelerate ion transport. The synergistic effects diarylamine units trinuclear copper clusters modulate local electron‐cloud density, regulating microenvironment ions ensuring nucleation. MCOF‐based separator's well‐defined 1D channels in separator enable uniform flux, promote resulting transference number 0.93 ionic conductivity 2.01 mS cm −1 at room temperature. Li|Cu cell demonstrates a barrier 16 mV, while symmetric exhibits stable plating/stripping over 1600 h 0.5 mA −2 . When coupled LiFePO 4 cathodes, assembled capacity retention ≈98%. work paves way dendrite‐free anodes high‐performance

Language: Английский

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Linkage-regulated covalent organic framework for low voltage near-infrared electrochromism and concealed information display

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Language: Английский

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