Computation-based regulation of excitonic effects in donor-acceptor covalent organic frameworks for enhanced photocatalysis

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 29, 2023

The strong excitonic effects widely exist in polymer-semiconductors and the large exciton binding energy (Eb) seriously limits their photocatalysis. Herein, density functional theory (DFT) calculations are conducted to assess band alignment charge transfer feature of potential donor-acceptor (D-A) covalent organic frameworks (COFs), using 1,3,5-tris(4-aminophenyl)triazine (TAPT) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) as acceptors tereph-thaldehydes functionalized diverse groups donors. Given discernable D-A interaction strengths pairs, Eb can be systematically regulated with minimum TAPT-OMe. Guided by these results, corresponding COFs synthesized, where TAPT-OMe-COF possesses best activity photocatalytic H2 production trend other is associated that calculated for pairs. In addition, further alkyne cycloaddition imine linkage greatly improves stability resulting TAPT-OMe-alkyne-COF a substantially smaller exhibits ~20 times higher than parent COF.

Language: Английский

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Construction of Covalent Organic Frameworks via Multicomponent Reactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(3), P. 1475 - 1496

Published: Jan. 16, 2023

Multicomponent reactions (MCRs) combine at least three reactants to afford the desired product in a highly atom-economic way and are therefore viewed as efficient one-pot combinatorial synthesis tools allowing one significantly boost molecular complexity diversity. Nowadays, MCRs no longer confined organic have found applications materials chemistry. In particular, can be used prepare covalent frameworks (COFs), which crystalline porous assembled from monomers exhibit broad range of properties applications. This synthetic approach retains advantages small-molecule MCRs, not only strengthening skeletal robustness COFs, but also providing additional driving forces for their crystallization, has been series robust COFs with diverse The present perspective article provides general background discusses types employed COF date, addresses related critical challenges future perspectives inspire MCR-based design new promote further progress this emerging field.

Language: Английский

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Covalent Organic Framework Nanobowls as Activatable Nanosensitizers for Tumor‐Specific and Ferroptosis‐Augmented Sonodynamic Therapy

Advanced Science, Journal Year: 2023, Volume and Issue: 10(6)

Published: Jan. 3, 2023

Abstract Covalent organic frameworks (COFs) have attracted increasing attention for biomedical applications. COFs‐based nanosensitizers with uniform nanoscale morphology and tumor‐specific curative effects are in high demand; however, their synthesis is yet challenging. In this study, distinct COF nanobowls synthesized a controlled manner engineered as activatable sonodynamic activity. High crystallinity ensures an ordered porous structure of the efficient loading small‐molecule sonosensitizer rose bengal (RB). To circumvent non‐specific damage to normal tissues, sonosensitization effect specifically inhibited by situ growth manganese oxide (MnO x ) on RB‐loaded COFs. Upon reaction tumor‐overexpressed glutathione (GSH), “gatekeeper” MnO rapidly decomposed recover reactive oxygen species (ROS) generation capability under ultrasound irradiation. Increased intracellular ROS stress GSH consumption concomitantly induce ferroptosis improve efficacy. Additionally, unconventional bowl‐shaped renders enhanced tumor accumulation retention. The combination therapy achieves efficacy killing cancer cells inhibiting growth. This study paves way development morphologies biomedicine, offering paradigm realize ferroptosis‐augmented therapy.

Language: Английский

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Monolayer-Assisted Surface-Initiated Schiff-Base-Mediated Aldol Polycondensation for the Synthesis of Crystalline sp² Carbon-Conjugated Covalent Organic Framework Thin Films

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 5203 - 5210

Published: Feb. 13, 2023

sp2 carbon-conjugated covalent organic frameworks (sp2c-COFs) with superb in-plane π-conjugations, high chemical stability, and robust framework structure are expected to be ideal films/membranes for a wide range of applications including energy-related devices optoelectronics. However, so far, sp2c-COFs have been mainly limited microcrystalline powders, this consequently hampered their performances in devices. Herein, we report simple methodology fabricate large-area, free-standing, crystalline sp2c-COF films (TFPT–TMT TB–TMT) on various solid substrates (e.g., fluorine-doped tin oxide, aluminum sheet, polyacrylonitrile membrane) by self-assembly monolayer-assisted surface-initiated Schiff-base-mediated aldol polycondensation (namely, SI-SBMAP). The resultant show lateral sizes up 120 cm2 tunable thickness from tens nanometers few micrometers. Owing the highly ordered quasi-1D channels, membrane-based osmotic power generator presents an output density 14.1 W m–2 under harsh conditions, outperforming most reported COF membranes as well commercialized benchmark (5 m–2). This work demonstrates interfacial fabrication green energy potential

Language: Английский

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Continuous Covalent Organic Frameworks Membranes: From Preparation Strategies to Applications

Small, Journal Year: 2023, Volume and Issue: 19(44)

Published: June 28, 2023

Abstract Covalent organic frameworks (COFs) are porous crystalline polymeric materials formed by the covalent bonding of units. The abundant units library gives COFs species diversity, easily tuned pore channels, and sizes. In addition, periodic arrangement endows regular highly connected which has led to rapid development in membrane separations. Continuous defect‐free high crystallinity COF membranes is key their application separations, most important issue be addressed research. This review article describes linkage types bonds, synthesis methods, size regulation strategies materials. Further, preparation continuous highlighted, including layer‐by‐layer (LBL) stacking, situ growth, interfacial polymerization (IP), solvent casting. applications separation fields also discussed, gas separation, water treatment, nanofiltration, ion conduction, energy battery membranes. Finally, research results summarized future prospect for outlined. More attention may paid large‐scale conductive

Language: Английский

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Photocatalytic CO2 reduction to syngas using metallosalen covalent organic frameworks

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 1, 2023

Abstract Metallosalen-covalent organic frameworks have recently gained attention in photocatalysis. However, their use CO 2 photoreduction is yet to be reported. Moreover, facile preparation of metallosalen-covalent with good crystallinity remains considerably challenging. Herein, we report a series produced via one-step synthesis strategy that does not require vacuum evacuation. possessing controllable coordination environments mononuclear and binuclear metal sites are obtained act as photocatalysts for tunable syngas production from . exhibit higher catalytic activities than those two-step synthesis. The optimal framework material containing cobalt triazine achieves rate 19.7 mmol g −1 h (11:8 H /CO), outperforming previously reported porous crystalline materials. This study provides producing high quality can accelerate exploration various applications.

Language: Английский

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Recent Advances in Rechargeable Metal–CO₂ Batteries with Nonaqueous Electrolytes

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(15), P. 9497 - 9564

Published: July 12, 2023

This review article discusses the recent advances in rechargeable metal-CO2 batteries (MCBs), which include Li, Na, K, Mg, and Al-based CO2 batteries, mainly with nonaqueous electrolytes. MCBs capture during discharge by reduction reaction release it charging evolution reaction. are recognized as one of most sophisticated artificial modes for fixation electrical energy generation. However, extensive research substantial developments required before appear reliable, sustainable, safe storage systems. The suffer from hindrances like huge charging-discharging overpotential poor cyclability due to incomplete decomposition piling insulating chemically stable compounds, carbonates. Efficient cathode catalysts a suitable architectural design essential address this issue. Besides, electrolytes also play vital role safety, ionic transportation, solid-electrolyte interphase formation, gas dissolution, leakage, corrosion, operational voltage window, etc. highly electrochemically active metals K anodes severely parasitic reactions dendrite formation. Recent works on aforementioned secondary have been categorically reviewed here, portraying latest findings key aspects governing MCB performances.

Language: Английский

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Catalytic Linkage Engineering of Covalent Organic Frameworks for the Oxygen Reduction Reaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 28, 2023

Metal-free covalent organic frameworks (COFs) have been employed to catalyze the oxygen reduction reaction (ORR). To achieve high activity and selectivity, various building blocks containing heteroatoms groups linked by imine bonds were used create catalytic COFs. However, roles of linkages COFs in ORR not investigated. In this work, linkage engineering has modulate behaviors. single sites while avoiding other possible sites, we synthesized from benzene units bonds, such as imine, amide, azine, oxazole bonds. Among these COFs, oxazole-linkage enables with highest activity, which achieved a half-wave potential 0.75 V limited current density 5.5 mA cm-2 . Moreover, oxazole-linked COF conversion frequency (TOF) value 0.0133 S-1 , 1.9, 1.3, 7.4-times that azine-, amide- imine-COFs, respectively. The theoretical calculation showed carbon atoms facilitated formation OOH* promoted protonation O* form OH*, thus advancing activity. This work guides us on are suitable for ORR.

Language: Английский

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Latest advances in layered covalent organic frameworks for water and wastewater treatment

Chemosphere, Journal Year: 2023, Volume and Issue: 329, P. 138580 - 138580

Published: April 3, 2023

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(3), P. 1904 - 1913

Published: Dec. 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.

Language: Английский

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