Structural Regulation of Covalent Organic Frameworks for Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(8), P. 1214 - 1226

Published: March 29, 2024

ConspectusChemical reactions can be promoted at lower temperatures and pressures, thereby reducing the energy input, by introducing suitable catalysts. Despite its significance, quest for efficient stable catalysts remains a significant challenge. In this context, addressing efficiency of stands out as paramount concern. However, challenges posed vague structure limited tailorability traditional would make it highly desirable to fabricate optimized based on understanding structure–activity relationships. Covalent organic frameworks (COFs), subclass fully designed crystalline materials formed polymerization building blocks through covalent bonds have garnered widespread attention in catalysis. The precise customizable structures COFs, coupled with attributes such high surface area facile functional modification, COFs attractive molecular platforms catalytic applications. These inherent advantages position ideal catalysts, facilitating elucidation structure-performance relationships further improving Nevertheless, there is lack systematic emphasis summary structural regulation atomic/molecular level COF Consequently, growing need summarize research field provide deep insights into COF-based catalysis promote development.In Account, we will recent advances achieved placing an design enhanced Considering unique components present fundamental principles rational This Account starts presenting overview explaining why are promising Then, introduce principle Next, following three aspects specific strategies catalysts: (1) By designing different groups integrating metal species unit, activity and/or selectivity finely modulated. (2) Regulating linkage facilitates charge transfer modulates electronic sites, accordingly, intrinsic activity/selectivity improved. (3) means pore wall/space engineering, microenvironment surrounding sites modulated optimize performance. Finally, current future developments discussed detail. provides insight toward their performance, which inspiration other heterogeneous

Language: Английский

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Simultaneous Protonation and Metalation of a Porphyrin Covalent Organic Framework Enhance Photodynamic Therapy

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16609 - 16618

Published: June 5, 2024

Covalent organic frameworks (COFs) have been explored for photodynamic therapy (PDT) of cancer, but their antitumor efficacy is limited by excited state quenching and low reactive oxygen species generation efficiency. Herein, we report a simultaneous protonation metalation strategy to significantly enhance the PDT nanoscale two-dimensional imine-linked porphyrin-COF. The neutral unmetalated porphyrin-COF (Ptp) protonated metalated (Ptp-Fe) were synthesized via imine condensation between 5,10,15,20-tetrakis(4-aminophenyl)porphyrin terephthalaldehyde in absence presence ferric chloride, respectively. chloride generated both doubly Fe3+-coordinated porphyrin units, which red-shifted increased Q-band absorption disrupted exciton migration prevent quenching, Under light irradiation, rapid energy transfer from porphyrins Ptp-Fe enabled 1O2 hydroxyl radical type II I processes. also catalyzed conversion hydrogen peroxide hydroxy through photoenhanced Fenton-like reaction under slightly acidic conditions illumination. As result, Ptp-Fe-mediated exhibited much higher cytotoxicity than Ptp-mediated on CT26 4T1 cancer cells. afforded potent subcutaneous murine colon orthotopic triple-negative breast tumors prevented metastasis lungs. This work underscores role fine-tuning molecular structures COFs enhancing efficacy.

Language: Английский

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Modulating the Microenvironments of Robust Metal Hydrogen‐Bonded Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 21, 2024

Abstract Hydrogen‐bonded organic frameworks (HOFs) are outstanding candidates for photocatalytic hydrogen evolution. However, most of reported HOFs suffer from poor stability and activity in the absence Pt cocatalyst. Herein, a series metal (Co 2 ‐HOF‐X, X=COOMe, Br, tBu OMe) have been rationally constructed based on dinuclear cobalt complexes, which exhibit exceptional presence strong acid (12 M HCl) base (5 NaOH) at least 10 days. More impressively, by varying ‐X groups microenvironment Co ‐HOF‐X can be modulated, giving rise to obviously different H production rates, following −X group sequence −COOMe>−Br>−tBu>−OMe. The optimized ‐HOF‐COOMe shows generation rate up 12.8 mmol g −1 h any additional noble‐metal photosensitizers cocatalysts, is superior Pt‐assisted systems. Experiments theoretical calculations reveal that grafted possess electron‐withdrawing ability, thus regulating electronic structures catalytic centres proton activation barrier production, leading distinctly activity.

Language: Английский

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A critical review of COFs-based photocatalysis for environmental remediation

Environmental Research, Journal Year: 2025, Volume and Issue: unknown, P. 121166 - 121166

Published: Feb. 1, 2025

Language: Английский

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Imine-linked 2D covalent organic frameworks based on benzotrithiophene for visible-light-driven selective aerobic sulfoxidation

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(12), P. 7036 - 7046

Published: Jan. 1, 2024

An imine-linked covalent organic framework based on benzotrithiophene generates superoxide and singlet oxygen to carry out blue-light-driven selective aerobic sulfoxidation.

Language: Английский

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Photochromic radical states in 3D covalent organic frameworks with zyg topology for enhanced photocatalysis

National Science Review, Journal Year: 2024, Volume and Issue: 11(7)

Published: May 21, 2024

Covalent-organic frameworks (COFs) with photoinduced donor-acceptor (D-A) radical pairs show enhanced photocatalytic activity in principle. However, achieving long-lived charge separation COFs proves challenging due to the rapid recombination. Here, we develop a novel strategy by combining [6 + 4] nodes construct

Language: Английский

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Mesoporous Vinylene‐Linked Covalent Organic Frameworks with Heteroatom‐Tuned Crystallinity and Photocatalytic Behaviors

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 15, 2024

Owing to its prominent π-delocalization and stability, vinylene linkage holds great merits in the construction of covalent organic frameworks (COFs) with promising semiconducting properties. However, carbon-carbon double bond formation reaction always exhibits relatively low reversibility, unfavorable for high crystalline through self-error correction assembling processes. In this work, we report a heteroatom-tuned strategy build up series two-dimensional (2D) vinylene-linked COFs by Knoevenagel condensation an electron-deficient methylthiazolyl-based monomer different triformyl substituted (hetero-)aromatic derivatives. The resulting show high-quality periodic mesoporous structures surface areas. Embedding heteroatoms into backbones enables significantly improving their crystallinity, finely tailoring structures. Upon visible light stimulation, one as-prepared donor-π-acceptor structure could deliver nearly seven-fold increase catalytic activity hydrogen generation as compared other two. Meanwhile, combination crystallinity matched conduction band energy level, such kind can be able selectively generate singlet oxygen superoxide radicals ratio 30 : 1, allowing catalyzing aerobic thioanisole oxidation distinctly tunable activities substituent electronic effect substrates.

Language: Английский

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The critical roles of surface-bound radicals in the nickel phosphide/biochar-persulfate catalytic oxidation system for tetracycline removal: The synergistic catalysis between nickel phosphides and biochar

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 491, P. 151915 - 151915

Published: May 6, 2024

Language: Английский

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Covalent Organic Frameworks as Heterogeneous Photocatalysts for Cross-Coupling Reactions

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(18), P. 9619 - 9651

Published: Jan. 1, 2024

This review focuses on advances in covalent organic framework (COF) photocatalysts for cross-coupling reactions, which provide a greener catalytic route transformations.

Language: Английский

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Delocalization Engineering of Heme‐Mimetic Artificial Enzymes for Augmented Reactive Oxygen Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 19, 2024

Abstract Developing artificial enzymes based on organic molecules or polymers for reactive oxygen species (ROS)‐related catalysis has broad applicability. Herein, inspired by porphyrin‐based heme mimics, we report the synthesis of polyphthalocyanine‐based conjugated (Fe‐PPc‐AE) as a new porphyrin‐evolving structure to serve efficient and versatile augmented catalysis. Owing structural advantages, such enhanced π‐conjugation networks π‐electron delocalization, promoted electron transfer, unique Fe−N coordination centers, Fe‐PPc‐AE showed more ROS‐production activity in terms Vmax turnover numbers compared with (Fe‐PPor‐AE), which also surpassed reported state‐of‐the‐art their activity. More interestingly, changing reaction medium substrates, revealed significantly improved environmental adaptivity many other ROS‐related biocatalytic processes, validating potential replace conventional (poly)porphyrin‐based mimics catalysis, biosensors, biotherapeutics. It is suggested that this study will offer essential guidance designing polymers.

Language: Английский

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