Confining and Highly Dispersing Single Polyoxometalate Clusters in Covalent Organic Frameworks by Covalent Linkages for CO₂ Photoreduction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(4), С. 1861 - 1871

Опубликована: Янв. 20, 2022

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion single-cluster catalyst is challenging. In this work, for first time, we present versatile strategy uniformly dispersed polyoxometalates (POMs) covalent organic frameworks (COFs) through confining POM cluster into regular nanopores COF by linkage. These COF-POM composites combine properties light absorption, electron transfer, and suitable catalytic active sites; as result, they exhibit outstanding activity artificial photosynthesis: that is, CO2 photoreduction with H2O donor. Among them, TCOF-MnMo6 achieved highest CO yield (37.25 μmol g-1 h-1 ca. 100% selectivity) gas-solid reaction system. Furthermore, mechanism study based on density functional theory (DFT) calculations demonstrated photoinduced transfer (PET) process occurs from to POM, then reduction oxidation occur COF, respectively. This work developed method single which also shows potential using materials photocatalysis.

Язык: Английский

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Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Фев. 27, 2023

Covalent organic frameworks (COFs) represent an emerging class of photocatalysts. However, their complicated structures lead to indeterminacy about photocatalytic active sites and reaction mechanisms. Herein, we use reticular chemistry construct a family isoreticular crystalline hydrazide-based COF photocatalysts, with the optoelectronic properties local pore characteristics COFs modulated using different linkers. The excited state electronic distribution transport pathways in are probed host experimental methods theoretical calculations at molecular level. One our developed (denoted as COF-4) exhibits remarkable electron utilization efficiency charge transfer properties, achieving record-high uranium extraction performance ~6.84 mg/g/day natural seawater among all techniques reported so far. This study brings new understanding operation COF-based guiding design improved photocatalysts for many applications.

Язык: Английский

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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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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6307 - 6416

Опубликована: Янв. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Язык: Английский

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Imine and imine-derived linkages in two-dimensional covalent organic frameworks

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(12), С. 881 - 898

Опубликована: Ноя. 11, 2022

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 Framework Based Functional Materials: Important Catalysts for Efficient CO₂Utilization

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(15)

Опубликована: Янв. 21, 2022

As hot topics in the chemical conversion of CO2 , photo-/electrocatalytic reduction and use as a supporter for energy storage have shown great potential utilization . However, many obstacles still exist on road to realizing highly efficient conversion, such inefficient uptake/activation mass transport catalysts. Covalent organic frameworks (COFs), kind porous material, been widely explored catalysts owing their unique features. In particular, COF-based functional materials containing diverse active sites (such single metal sites, nanoparticles, oxides) offer storage. This Minireview discusses recent breakthroughs basic knowledge, mechanisms, pathways strategies that addition, challenges prospects are also introduced.

Язык: Английский

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Scalable Synthesis of Ultrathin Polyimide Covalent Organic Framework Nanosheets for High-Performance Lithium–Sulfur Batteries

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(46), С. 19446 - 19453

Опубликована: Ноя. 3, 2021

Development of new porous materials as hosts to suppress the dissolution and shuttle lithium polysulfides is beneficial for constructing highly efficient lithium-sulfur batteries (LSBs). Although 2D covalent organic frameworks (COFs) host exhibit promising potential LSBs, their performance still not satisfactory. Herein, we develop polyimide COFs (PI-COF) with a well-defined lamellar structure, which can be exfoliated into ultrathin (∼1.2 nm) nanosheets (PI-CONs) large size (∼6 μm) quantity (40 mg/batch). Explored sulfur PI-COF PI-CONs deliver high capacities (1330 1205 mA h g-1 at 0.1 C, respectively), excellent rate capabilities (620 503 4 superior cycling stability (96% capacity retention 0.2 C PI-CONs) by virtue synergy robust conjugated strong oxygen-lithium interactions, surpassing vast majority organic/polymeric battery cathodes ever reported. Our finding demonstrates that COF carbonyl groups could LSBs electrochemical performance.

Язык: Английский

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Linkage-engineered donor–acceptor covalent organic frameworks for optimal photosynthesis of hydrogen peroxide from water and air

Nature Catalysis, Год журнала: 2024, Номер 7(2), С. 195 - 206

Опубликована: Фев. 13, 2024

Язык: Английский

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Conjugated microporous polymers for energy storage: Recent progress and challenges

Nano Energy, Год журнала: 2021, Номер 85, С. 105958 - 105958

Опубликована: Март 7, 2021

Язык: Английский

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