Three-Component Donor−π–Acceptor Covalent–Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8364 - 8374

Опубликована: Март 14, 2023

Two-dimensional covalent-organic frameworks (2D COFs) have recently emerged as great prospects for their applications new photocatalytic platforms in solar-to-hydrogen conversion; nevertheless, inefficient solar energy capture and fast charge recombination hinder the improvement of hydrogen production performance. Herein, two photoactive three-component donor-π-acceptor (TCDA) materials were constructed using a multicomponent synthesis strategy by introducing electron-deficient triazine electron-rich benzotrithiophene moieties into through sp2 carbon imine linkages, respectively. Compared with two-component COFs, novel TCDA-COFs are more convenient regulating inherent photophysical properties, thereby realizing outstanding activity evolution from water. Remarkably, first carbon-linked TCDA-COF displays an impressive rate 70.8 ± 1.9 mmol g-1 h-1 excellent reusability presence 1 wt % Pt under visible-light illumination (420-780 nm). Utilizing combination diversified spectroscopy theoretical prediction, we show that full π-conjugated linkage not only effectively broadens harvesting COFs but also enhances transfer separation efficiency.

Язык: Английский

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Tuning Local Charge Distribution in Multicomponent Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Uranium Extraction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Апрель 29, 2023

Optimizing the electronic structure of covalent organic framework (COF) photocatalysts is essential for maximizing photocatalytic activity. Herein, we report an isoreticular family multivariate COFs containing chromenoquinoline rings in COF and electron-donating or withdrawing groups pores. Intramolecular donor-acceptor (D-A) interactions allowed tuning local charge distributions carrier separation under visible light irradiation, resulting enhanced performance. By optimizing optoelectronic properties COFs, a uranium extraction efficiency 8.02 mg/g/day was achieved using nitro-functionalized multicomponent natural seawater, exceeding performance all reported to date. Results demonstrate effective design strategy towards high-activity with intramolecular D-A structures not easily accessible traditional synthetic approaches.

Язык: Английский

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Covalent Organic Frameworks for Energy Conversion in Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(34)

Опубликована: Апрель 24, 2023

Abstract Intensifying energy crises and severe environmental issues have led to the discovery of renewable sources, sustainable conversion, storage technologies. Photocatalysis is a green technology that converts eco‐friendly solar into high‐energy chemicals. Covalent organic frameworks (COFs) are porous materials constructed by covalent bonds show promising potential for converting chemicals owing their pre‐designable structures, high crystallinity, porosity. Herein, we highlight recent progress in synthesis COF‐based photocatalysts applications water splitting, CO 2 reduction, H O production. The challenges future opportunities rational design COFs advanced discussed. This Review expected promote further development toward photocatalysis.

Язык: Английский

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Covalent organic frameworks towards photocatalytic applications: Design principles, achievements, and opportunities

Coordination Chemistry Reviews, Год журнала: 2022, Номер 475, С. 214882 - 214882

Опубликована: Окт. 14, 2022

Язык: Английский

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Electronic Transmission Channels Promoting Charge Separation of Conjugated Polymers for Photocatalytic CO₂ Reduction with Controllable Selectivity

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Апрель 3, 2023

Conjugated polymers (CPs) represent a promising platform for photocatalytic CO2 fixation owing to their suitable band structures that meet the requirements of reduction potential value-added fuels. However, performance CPs is rather restrained by low charge transfer efficiency. Herein, we rationally designed three with more delocalized electronic transmission channel and planar molecular structure, which are regarded evidently reduce exciton binding energy (Eb ) accelerate internal process. Besides, assembly electron-output "tentacles" cocatalysts on surface could effectively facilitate interfacial electron delivery. Accordingly, optimal P-2CN exhibits an apparent quantum yield 4.6 % at 420 nm CO. Further adjusting amounts cyano groups cocatalysts, CO selectivity be obtained in range 0-80.5 %.

Язык: Английский

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Enhancement of Visible‐Light‐Driven Hydrogen Evolution Activity of 2D π‐Conjugated Bipyridine‐Based Covalent Organic Frameworks via Post‐Protonation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 9, 2023

Photocatalytic hydrogen (H2 ) evolution represents a promising and sustainable technology. Covalent organic frameworks (COFs)-based photocatalysts have received growing attention. A 2D fully conjugated ethylene-linked COF (BTT-BPy-COF) was fabricated with dedicated designed active site. The introduced bipyridine sites enable facile post-protonation strategy to fine-tune the actives sites, which results in largely improved charge-separation efficiency increased hydrophilicity pore channels synergically. After modulating degree of protonation, optimal BTT-BPy-PCOF exhibits remarkable H2 rate 15.8 mmol g-1 h-1 under visible light, surpasses biphenyl-based 6 times. By using different types acids, is proved be potential universal for promoting photocatalytic evolution. This would provide important guidance design highly efficient semiconductor photocatalysts.

Язык: Английский

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

Materials Chemistry Frontiers, Год журнала: 2023, Номер 7(16), С. 3298 - 3331

Опубликована: Янв. 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.

Язык: Английский

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Recent Progress of Covalent Organic Frameworks‐Based Materials in Photocatalytic Applications: A Review

Small, Год журнала: 2023, Номер 19(48)

Опубликована: Авг. 4, 2023

Abstract Covalent organic frameworks (COFs) are one type of porous materials linked by covalent bonds. COFs exhibit many outstanding characteristics such as high porosity, chemical and thermal stability, large specific surface area, efficient electron transfer efficiency, the ability for predesigned structures. These exceptional advantages enable to remarkable performance in photocatalysis. Additionally, activity photocatalysts can be significantly upgraded ion doping formation heterojunctions. This paper summarizes latest research progress on COF‐based applied photocatalytic systems. Initially, typical structures preparation methods analyzed compared. Moreover, essential principles reactions over COFs‐based developments hydrogen production, CO 2 reduction, pollutants elimination, transformation, overall water splitting indicated. At last, outlook challenges photocatalysis discussed. review is intended permit instructive guidance use based future.

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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Weakly Hydrophilic Imine-Linked Covalent Benzene–Acetylene Frameworks for Photocatalytic H₂O₂ Production in the Two-Phase System

ACS Applied Materials & Interfaces, Год журнала: 2023, Номер 15(6), С. 8066 - 8075

Опубликована: Фев. 1, 2023

Conversing oxygen (O2) to hydrogen peroxide (H2O2) driven by solar energy is a promising H2O2 onsite production route but often short of efficient and durable photocatalysts. Herein, strong π-π conjugate polycyclic aromatic benzene acetylene units have been constructed into new covalent organic frameworks (COFs) linked imine C═N bonding. These COFs demonstrated two-dimensional hexagonal crystalline with higher crystallinity larger surface area (>600 m2 g-1). Covalent benzene-acetylene possessed appropriate visible light-responsive band structure the suppressed charge recombination rate. The -OH groups on their enable them be weakly hydrophilic. As result, it served as high-performance photocatalysts for in water-benzyl alcohol (BA) two-phase system. It delivered rate 1240 μmol h-1 gcat-1 catalytic efficiency within 60 h, comparable best COF-based catalysts. This study provides an photocatalytic system based hydrophilic imine-linked

Язык: Английский

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