Bulk COFs and COF nanosheets for electrochemical energy storage and conversion

Chemical Society Reviews, Год журнала: 2020, Номер 49(11), С. 3565 - 3604

Опубликована: Янв. 1, 2020

The current advances, structure-property relationship and future perspectives in covalent organic frameworks (COFs) their nanosheets for electrochemical energy storage (EES) conversion (EEC) are summarized.

Язык: Английский

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Covalent organic frameworks: an ideal platform for designing ordered materials and advanced applications

Chemical Society Reviews, Год журнала: 2020, Номер 50(1), С. 120 - 242

Опубликована: Дек. 7, 2020

Covalent organic frameworks offer a molecular platform for integrating units into periodically ordered yet extended 2D and 3D polymers to create topologically well-defined polygonal lattices built-in discrete micropores and/or mesopores.

Язык: Английский

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Polymer photocatalysts for solar-to-chemical energy conversion

Nature Reviews Materials, Год журнала: 2020, Номер 6(2), С. 168 - 190

Опубликована: Ноя. 5, 2020

Язык: Английский

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Solving the COF trilemma: towards crystalline, stable and functional covalent organic frameworks

Chemical Society Reviews, Год журнала: 2020, Номер 49(23), С. 8469 - 8500

Опубликована: Янв. 1, 2020

Covalent organic frameworks (COFs) have entered the stage as a new generation of porous polymers which stand out by virtue their crystallinity, diverse framework topologies and accessible pore systems. An important - but still underdeveloped feature COFs is potentially superior stability in comparison to other materials. Achieving are simultaneously crystalline, stable, functional challenging reversible bond formation one prime prerequisites for crystallization COFs. However, COF field matures strategies surfaced that bypass this crystallinity dichotomy. Three major approaches obtaining both stable crystalline taken form recent years: Tweaking reaction conditions linkages, separating order inducing step step, controlling structural degrees freedom during assembly final COF. This review discusses rational engineering COFs, apt at overcoming current challenges design open up avenues real-world applications

Язык: Английский

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Metal–Organic Framework-Based Enzyme Biocomposites

Chemical Reviews, Год журнала: 2021, Номер 121(3), С. 1077 - 1129

Опубликована: Янв. 13, 2021

Because of their efficiency, selectivity, and environmental sustainability, there are significant opportunities for enzymes in chemical synthesis biotechnology. However, as the three-dimensional active structure is predominantly maintained by weaker noncovalent interactions, thermal, pH, stressors can modify or eliminate activity. Metal–organic frameworks (MOFs), which extended porous network materials assembled a bottom-up building block approach from metal-based nodes organic linkers, be used to afford protection enzymes. The self-assembled structures MOFs encase an enzyme process called encapsulation when MOF synthesized presence biomolecule. Alternatively, infiltrated into mesoporous surface bound via covalent processes. Integration this way affords allows maintain activity challenge conditions (e.g., denaturing agents, elevated temperature, non-native solvents). In addition forming simple enzyme/MOF biocomposites, other introduced composites improve recovery facilitate advanced applications sensing fuel cell technology. This review canvasses encapsulation, pore infiltration, adsorption summarizes strategies form multicomponent composites. Also, given that biocomposites straddle chemistry enzymology, provides assessment characterization methodologies MOF-immobilized identifies some key parameters development field.

Язык: Английский

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New synthetic strategies toward covalent organic frameworks

Chemical Society Reviews, Год журнала: 2020, Номер 49(10), С. 2852 - 2868

Опубликована: Янв. 1, 2020

This tutorial review highlights the representative advances in new synthetic strategies toward covalent organic frameworks.

Язык: Английский

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Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(49), С. 20763 - 20771

Опубликована: Ноя. 23, 2020

Excitonic effects caused by Coulomb interactions between electrons and holes play subtle significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals porphyrin centers, shown as ideal models to regulate excitonic effects. Remarkably, incorporation Zn2+ COF facilitates conversion singlet triplet excitons, whereas Ni2+ introduction promotes dissociation excitons hot carriers under photoexcitation. Accordingly, discriminative behavior DhaTph-Zn DhaTph-Ni enables activation O2 1O2 O2•–, respectively, visible light irradiation, resulting distinctly activity selectivity photocatalytic terpinene oxidation. Benefiting from these results, exhibits excellent O2•–-engaged hydroxylation boronic acid, while possesses superior performance 1O2-mediated selective oxidation sulfides. This work provides in-depth insights into molecular oxygen opens an avenue regulation based COFs.

Язык: Английский

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Regulating Photocatalysis by Spin-State Manipulation of Cobalt in Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(39), С. 16723 - 16731

Опубликована: Сен. 7, 2020

While catalysis is highly dependent on the electronic structure of catalyst, understanding catalytic performance affected by electron spin regulation remains challenging and rare. Herein, we have developed a facile strategy to manipulation cobalt state over covalent organic frameworks (COFs), COF-367-Co, simply changing oxidation Co centered in porphyrin. Density functional theory (DFT) calculations together with experimental results confirm that CoII CoIII are embedded COF-367 S = 1/2 0 ground states, respectively. Remarkably, photocatalytic CO2 reduction indicate COF-367-CoIII exhibits favorable activity significantly enhanced selectivity HCOOH, accordingly much reduced CO CH4, sharp contrast COF-367-CoII. The highlight spin-state transition greatly regulates performance. Theoretical further disclose presence COF-367-Co preferable formation HCOOH but detrimental its conversion, which clearly accounts for distinctly different photocatalysis To best our knowledge, this first report regulating COFs.

Язык: Английский

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Rational design of isostructural 2D porphyrin-based covalent organic frameworks for tunable photocatalytic hydrogen evolution

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Март 1, 2021

Abstract Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be beneficial for the structural design, is still far-away explored. Herein, we report designed synthesis of four isostructural porphyrinic two-dimensional covalent (MPor-DETH-COF, M = H 2 , Co, Ni, Zn) and activity generation. Our results clearly show that all adopt AA stacking structures, with high crystallinity large surface area. Interestingly, incorporation different transition metals into porphyrin rings can rationally tune evolution rate corresponding frameworks, order CoPor-DETH-COF < Por-DETH-COF NiPor-DETH-COF ZnPor-DETH-COF. Based on detailed experiments calculations, this tunable performance mainly explained by tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple effective way efficient tuning activities at level, but also provides valuable insight structure design better photocatalysis.

Язык: Английский

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Two-dimensional covalent organic frameworks with hierarchical porosity

Chemical Society Reviews, Год журнала: 2020, Номер 49(12), С. 3920 - 3951

Опубликована: Янв. 1, 2020

This review highlights the state-of-the-art progress achieved in two-dimensional covalent organic frameworks (COFs) with hierarchical porosity, an emerging class of COFs constructed by integrating different types pores into one framework.

Язык: Английский

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