Active Site Engineering in Reticular Covalent Organic Frameworks for Photocatalytic CO₂ Reduction

Advanced Functional Materials, Год журнала: 2023, Номер 34(43)

Опубликована: Окт. 15, 2023

Abstract Photochemical CO 2 reduction using ubiquitous sunlight akin to natural photosynthesis is an effective approach for conversion of renewable energy into useful chemical feedstock. Driven by the need earth‐abundant, inexpensive, and sustainable photocatalysts with practical applicability, covalent organic frameworks (COFs) have emerged as a new generation molecularly defined semiconductors tunable optoelectronic properties. These reticular highly ordered, porous crystalline structures can be tailor‐made covalently combining building blocks target specific functions. To date, numerous COFs been reported, which show promising activity photocatalytic allowing derive structure–property–function relationships. In this review, different reported strategies are comprehensively analyzed categorized active site engineering in COF synthetic rationale resulting catalytic each discussed. The recent advancements terms tailored photocatalyst design then critically assessed, aspects advanced materials characterization analyzed, future perspectives challenges field highlighted.

Язык: Английский

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Structural Regulation of Covalent Organic Frameworks for Catalysis

Accounts of Chemical Research, Год журнала: 2024, Номер 57(8), С. 1214 - 1226

Опубликована: Март 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

Язык: Английский

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Three-dimensional covalent organic frameworks with nia nets for efficient separation of benzene/cyclohexane mixtures

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 27, 2024

Abstract The synthesis of three-dimensional covalent organic frameworks with highly connected building blocks presents a significant challenge. In this study, we report two 3D COFs the nia topology, named JUC-641 and JUC-642, by introducing planar hexagonal triangular prism nodes. Notably, our adsorption studies breakthrough experiments reveal that both exhibit exceptional separation capabilities, surpassing previously reported most porous polymers, factor up to 2.02 for benzene cyclohexane. Additionally, dispersion-corrected density functional theory analysis suggests good performance these can be attributed incorporation aromatic presence extensive pore structures. Consequently, research not only expands diversity but also highlights potential COF materials as promising candidates environmentally-friendly applications.

Язык: Английский

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Facilely tunable dodecahedral polyoxometalate framework loaded with mono- or bimetallic sites for efficient photocatalytic CO2 reduction

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 346, С. 123733 - 123733

Опубликована: Янв. 14, 2024

Язык: Английский

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Porphyrin-based MOFs for photocatalysis in water: advancements in solar fuels generation and pollutants degradation

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер 11(8), С. 2212 - 2245

Опубликована: Янв. 1, 2024

This review highlights the recent advances in photocatalytic applications of porphyrin-based MOFs aqueous environments for solar fuel generation and water remediation.

Язык: Английский

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Stepwise Protonation of Three‐Dimensional Covalent Organic Frameworks for Enhancing Hydrogen Peroxide Photosynthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)

Опубликована: Май 13, 2024

Abstract Three‐dimensional covalent organic frameworks (3D COFs), recognized for their tailorable structures and accessible active sites, offer a promising platform developing advanced photocatalysts. However, the difficulty in synthesis functionalization of 3D COFs hinders further development. In this study, we present series 3D‐ bcu ‐COFs with 8 connected porphyrin units linked by linear linkers through imine bonds as versatile photocatalyst design. The photoresponse was initially modulated functionalizing benzo‐thiadiazole or benzo‐selenadiazole groups. Furthermore, taking advantage well‐exposed sites ‐COFs, photocatalytic activity optimized stepwise protonation centers. dual protonated COF groups exhibited enhanced charge separation, leading to an increased H 2 O production under visible light. This enhancement demonstrates combined benefits linker on efficiency.

Язык: Английский

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Molecular Engineering for Modulating Photocatalytic Hydrogen Evolution of Fully Conjugated 3D Covalent Organic Frameworks

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 16, 2024

Covalent organic frameworks (COFs) have recently shown great potential for photocatalytic hydrogen production. Currently almost all reports are focused on two-dimensional (2D) COFs, while the 3D counterparts rarely explored due to their non-conjugated derived from sp

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)

Опубликована: Сен. 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

Язык: Английский

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12 Connecting Sites Linked Three‐dimensional Covalent Organic Frameworks with Intrinsic Non‐interpenetrated shp Topology for Photocatalytic H₂O₂ Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Фев. 9, 2024

Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting building blocks. This however represents most important step promoting diversity of COFs due still limited dynamic bonds available for constructing at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D MPc-THHI-COFs (M=H

Язык: Английский

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Recent progress on covalent organic frameworks and their composites as electrode materials for supercapacitors

Advanced Composites and Hybrid Materials, Год журнала: 2024, Номер 8(1)

Опубликована: Дек. 26, 2024

Язык: Английский

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