Reticular framework materials for photocatalytic organic reactions

Chemical Society Reviews, Год журнала: 2023, Номер 52(22), С. 7949 - 8004

Опубликована: Янв. 1, 2023

Photocatalytic organic reactions, harvesting solar energy to produce high value-added chemicals, have attracted increasing attention as a sustainable approach address the global crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) covalent (COFs), are widely considered promising candidates for photocatalysis owing their crystallinity, tailorable pore environment extensive structural diversity. Although design synthesis of MOFs COFs been intensively developed in last 20 years, applications photocatalytic transformations still preliminary stage, making systematic summary necessary. Thus, this review aims provide comprehensive understanding useful guidelines exploration suitable MOF COF photocatalysts towards appropriate reactions. The commonly used reactions categorized facilitate identification reaction types. From practical viewpoint, fundamentals experimental design, active species, performance evaluation external conditions, discussed detail easy experimentation. Furthermore, latest advances COFs, composites, comprehensively summarized according actual sites, together with discussion structure-property relationship. We believe that study will be helpful researchers novel reticular various synthetic applications.

Язык: Английский

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Nanoarchitectonics of Hollow Covalent Organic Frameworks: Synthesis and Applications

ACS Nano, Год журнала: 2023, Номер 17(10), С. 8918 - 8934

Опубликована: Май 2, 2023

Hollow covalent organic frameworks (COFs) have gained significant attention because of their specific properties, including enhanced surface-to-volume ratio, large surface area, hierarchical structure, highly ordered nanostructures, and excellent chemical stability. These intrinsic characteristics endow hollow COFs with fascinating physicochemical properties make them attractive for widespread applications, such as catalysis, energy storage, drug delivery, therapy, sensing, environmental remediation. This review focuses on the recent developments in synthesis derivatives. In addition, practical applications various fields are summarized. Finally, challenges future opportunities terms synthetic methodologies discussed. expected to play an important role materials science.

Язык: Английский

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A Tailored COF for Visible-Light Photosynthesis of 2,3-Dihydrobenzofurans

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 5074 - 5082

Опубликована: Фев. 24, 2023

Heterogeneous photocatalysis is considered as an ecofriendly and sustainable approach for addressing energy environmental persisting issues. Recently, heterogeneous photocatalysts based on covalent organic frameworks (COFs) have gained considerable attention due to their remarkable performance recyclability in photocatalytic transformations, offering a prospective alternative homogeneous precious metal/organic dyes. Herein, we report Hex-Aza-COF-3 metal-free, visible-light-activated, reusable photocatalyst the synthesis of 2,3-dihydrobenzofurans, pharmaceutically relevant structural motif, via selective oxidative [3+2] cycloaddition phenols with olefins. Moreover, demonstrate natural products (±)-conocarpan (±)-pterocarpin reaction important step using photocatalyst. Interestingly, presence phenazine hexaazatriphenylene rigid heterocyclic units strengthens linkages, enhances absorption visible region, narrows band, leading excellent activity, charge transport, stability, reactions, evident from theoretical calculations real-time information ultrafast spectroscopic measurements.

Язык: Английский

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Structural Motifs in Covalent Organic Frameworks for Photocatalysis

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Март 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

Язык: Английский

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Metal–organic frameworks for organic transformations by photocatalysis and photothermal catalysis

Chemical Society Reviews, Год журнала: 2024, Номер 53(18), С. 9378 - 9418

Опубликована: Янв. 1, 2024

Organic transformation by light-driven catalysis, especially, photocatalysis and photothermal denoted as photo(thermal) is an efficient, green, economical route to produce value-added compounds. In recent years, owing their diverse structure types, tunable pore sizes, abundant active sites, metal-organic framework (MOF)-based catalysis has attracted broad interest in organic transformations. this review, we provide a comprehensive systematic overview of MOF-based for First, the general mechanisms, unique advantages, strategies improve performance MOFs are discussed. Then, outstanding examples transformations over introduced according reaction type. addition, several representative advanced characterization techniques used revealing charge kinetics intermediates presented. Finally, prospects challenges field proposed. This review aims inspire rational design development materials with improved catalysis.

Язык: Английский

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Construction of a 2D/2D Crystalline Porous Materials Based S‐Scheme Heterojunction for Efficient Photocatalytic H₂ Production

Advanced Energy Materials, Год журнала: 2024, Номер 14(11)

Опубликована: Янв. 7, 2024

Abstract Generally, the low electron–hole separation efficiency of covalent organic frameworks (COFs) prevents their catalytic performance from reaching satisfactory results. For this reason, creation heterojunctions is considered an effective strategy but usually suffers dimensional mismatch integrated material, even at expense its redox capacity. To overcome these difficulties, a novel 2D/2D S‐scheme heterojunction between H 2 N–Cu–MOF (NCM) and TpPa–1–COF (TP1C) successfully constructed for efficient photocatalytic production. The matching dimensions two crystalline porous materials enables with abundant surface reactive sites, strong interaction optimized electronic structure. Moreover, combination can also form S–scheme heterojunction, which not only promote pair, preserve ability, thus remarkably boosting competence. Consequently, rate optimal 20% NCM/TP1C in production reaches 4.19 mmol g −1 h , 46.5 times higher than that bare NCM, 22.1 folds over pure TP1C. This research offers innovative perspective formation based on crystal solar energy utilization.

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(3), С. 1904 - 1913

Опубликована: Дек. 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.

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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Protonation of an Imine‐linked Covalent Organic Framework for Efficient H₂O₂ Photosynthesis under Visible Light up to 700 nm

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 13, 2024

Abstract Covalent organic frameworks (COFs) are promising photocatalysts for H 2 O production from water via oxygen reduction reaction (ORR). The design of COFs efficient indubitably hinges on an in‐depth understanding their ORR mechanisms. In this work, taking imine‐linked COF as example, we demonstrate that protonation the functional units such imine, amine, and triazine, is a highly strategy to upgrade activity levels synthesis. not only extends light absorption but also provides proton sources directly participate in generation. Notably, simplifies pathways , i.e. indirect superoxide radical ( ) mediated route direct one‐step two‐electron route. Theoretical calculations confirm favors synthesis due easy access protons near sites removes energy barrier generating *OOH intermediate. These findings extend mechanistic insight into photosynthesis provide rational guideline upgradation COFs.

Язык: Английский

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Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Generation

ACS Materials Letters, Год журнала: 2024, Номер 6(5), С. 2007 - 2049

Опубликована: Апрель 17, 2024

Hydrogen peroxide (H2O2), a valuable chemical, is widely used as powerful oxidizing agent in chemical synthesis, pharmaceuticals, medical disinfection, and environmental treatment industries. Currently, over 95% of H2O2 produced industrially using the anthraquinone process, which associated with its high energy consumption hazardous byproducts. Therefore, photochemical synthesis from water oxygen covalent organic framework based photocatalysts have attracted considerable attention. This review aims to outline recent achievements, challenges future prospects COFs heterogeneous for sustainable generation. We summarize chronological development COFs, different mechanisms involved, detailed experiments quantification methods photocatalytic The puts forward an outlook, highlighting advantages limitations anticipate that this will provide insight into current progress inspire next-generation production.

Язык: Английский

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