Three-Dimensional Covalent Organic Frameworks with Ultra-Large Pores for Highly Efficient Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 3248 - 3254

Published: Jan. 31, 2023

Benefiting from their unique structural merits, three-dimensional (3D) large-pore COF materials demonstrate high surface areas and interconnected large channels, which makes these promising in practical applications. Unfortunately, functionalization strategies application research are still absent structures. To this end, a series of functional 3D stp-topologized COFs designed based on porphyrin or metalloporphyrin moieties, named JUC-640-M (M = Co, Ni, H). Interestingly, JUC-640-H exhibits record-breaking low crystal density (0.106 cm3 g-1) among all crystalline materials, along with the largest pore size (4.6 nm) COFs, area (2204 m2 g-1), abundant exposed moieties (0.845 mmol g-1). Inspired by characteristics photoelectrical performance, JUC-640-Co is utilized for photoreduction CO2 to CO demonstrates production rate (15.1 g-1 h-1), selectivity (94.4%), stability. It should be noted that has exceeded those reported COF-based materials. This work not only produces novel channels but also provides new guidance applications COFs.

Language: Английский

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Covalent Organic Frameworks Enable Sustainable Solar to Hydrogen Peroxide

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(12)

Published: Dec. 6, 2023

Abstract As a chemical product with rapidly expanding demand in the field of modern energy and environmental applications, hydrogen peroxide (H 2 O ) has garnered widespread attention. However, existing industrial production H is plagued by high consumption, harmful waste emission, severe safety issues, making it difficult to satisfy environmental/economic concept. Artificial photosynthesis offers viable strategy for green sustainable since uses sunlight as an source initiate reaction oxygen water produce . Among various photocatalysts, covalent organic frameworks (COFs), featuring highly ordered skeletons well‐defined active sites, have emerged promising photocatalysts production. This review presents nascent burgeoning area photocatalytic based on COFs. First, brief overview technology provided, followed detailed introduction principles evaluation generation. Subsequently, latest research progress judicious design COFs expounded, particular emphasis manipulating electronic structures redox sites. Finally, outlook challenges future opportunities proposed, hope stimulating further explorations novel molecular‐designed photosynthesis.

Language: Английский

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Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4951 - 4956

Published: Feb. 27, 2023

Multicomponent reactions (MCRs), as a powerful one-pot combinatorial synthesis tool, have been recently applied to the of covalent organic frameworks (COFs). Compared with thermally driven MCRs, photocatalytic MCR-based COF has not yet investigated. Herein, we first report construction COFs by multicomponent reaction. Upon visible-light irradiation, series excellent crystallinity, stability, and permanent porosity are successfully synthesized via photoredox-catalyzed Petasis reaction under ambient conditions. Additionally, obtained Cy-N3-COF exhibits photoactivity recyclability for visible-light-driven oxidative hydroxylation arylboronic acids. The concept polymerization only enriches methodology but also opens new avenue that might be possible existing synthetic methods based on MCRs.

Language: Английский

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Covalent organic frameworks for CO₂ capture: from laboratory curiosity to industry implementation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(18), P. 6294 - 6329

Published: Jan. 1, 2023

Synergistic developments of covalent organic frameworks and engineering processes can expedite the qualitative leap for net-zero carbon emissions.

Language: Английский

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Covalent organic frameworks in heterogeneous catalysis: recent advances and future perspective

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(16), P. 3298 - 3331

Published: Jan. 1, 2023

This review provides an overview of the recent advances in heterogeneous catalysis using COFs, primarily from 2020 to 2023, covering fundamentals, advantages, current challenges, and future perspectives.

Language: Английский

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Recent Progress on Phase Engineering of Nanomaterials

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(23), P. 13489 - 13692

Published: Nov. 14, 2023

As a key structural parameter, phase depicts the arrangement of atoms in materials. Normally, nanomaterial exists its thermodynamically stable crystal phase. With development nanotechnology, nanomaterials with unconventional phases, which rarely exist their bulk counterparts, or amorphous have been prepared using carefully controlled reaction conditions. Together these methods are beginning to enable engineering (PEN), i.e., synthesis phases and transformation between different obtain desired properties functions. This Review summarizes research progress field PEN. First, we present representative strategies for direct modulation diverse kinds nanomaterials. We cover ranging from metal nanostructures such as Au, Ag, Cu, Pd, Ru, alloys; oxides, borides, carbides; transition dichalcogenides (TMDs) 2D layered review growth wet-chemical reduction seed-mediated epitaxial chemical vapor deposition (CVD), high pressure transformation, electron ion-beam irradiation. After that, summarize significant influence on various unconventional-phase also discuss potential applications developed areas including catalysis, electrochemical energy storage (batteries supercapacitors), solar cells, optoelectronics, sensing. Finally, existing challenges future directions

Language: Английский

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Strategic design of covalent organic frameworks (COFs) for photocatalytic hydrogen generation

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(27), P. 14489 - 14538

Published: Jan. 1, 2023

Covalent organic frameworks provide a platform for the integration of functional linkers into ordered yet tunable two-dimensional to yield π–π stacked conjugated materials photocatalytic water splitting hydrogen generation.

Language: Английский

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3D covalent organic framework membrane with fast and selective ion transport

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

Published: Sept. 22, 2023

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able break the trade-off between ion conductivity and selectivity, waiting for exploitation. Herein, we report fabrication of a sulfonic acid-functionalized COF membrane (3D SCOF) efficient selective transport, using dual acid-mediated interfacial polymerization strategy. The SCOF membranes possess highly interconnected transport channels, ultramicroporous pore sizes (0.97 nm), abundant sulfonate groups (with high exchange capacity 4.1 mmol g-1), leading proton 843 mS cm-1 at 90 °C. When utilized in osmotic energy conversion, power density 21.2 W m-2, remarkable selectivity 0.976 thus an exceptional conversion efficiency 45.3% simultaneously achieved. This work provides alternative approach promotes applications COFs separation.

Language: Английский

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Structural Motifs in Covalent Organic Frameworks for Photocatalysis

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

Published: March 10, 2024

Abstract Covalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion transmission of photogenerated charges during photocatalysis. Currently, a considerable number COFs are used as metal‐free semiconductor photocatalysts. This review aims understand relationships between structure photocatalysis performance provides in‐depth insight into synthetic strategy improve performance. Subsequently, focuses on structural motif in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, peroxide generation, compound transformations. Last, conjunction with progress achieved challenges yet be overcome, candid discussion is undertaken regarding field COF photocatalysis, accompanied by presentation potential research avenues future directions. seeks provide readers comprehensive understanding pivotal role robust guidance innovative utilization

Language: Английский

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Record Ultralarge‐Pores, Low Density Three‐Dimensional Covalent Organic Framework for Controlled Drug Delivery**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Jan. 23, 2023

Abstract The unique structural characteristics of three‐dimensional (3D) covalent organic frameworks (COFs) like high surface areas, interconnected pore system and readily accessible active sites render them promising platforms for a wide set functional applications. Albeit promising, the reticular construction 3D COFs with large pores is very demanding task owing to formation interpenetrated frameworks. Herein we report designed synthesis non‐interpenetrated stp net COF, namely TUS‐64, largest size all (47 Å) record‐low density (0.106 g cm −3 ) by reticulating 6‐connected triptycene‐based linker 4‐connected porphyrin‐based linker. Characterized highly mesoporous scaffold good stability, TUS‐64 shows efficient drug loading controlled release five different drugs in simulated body fluid environment, demonstrating competency as nanocarriers.

Language: Английский

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