Mechanisms of Defect Correction by Reversible Chemistries in Covalent Organic Frameworks

Zhu, Yunlong; Zhao, Huanyu; Fu, Cui-Liu; Li, Zhanwei; Sun, Zhao-Yan; Lu, Zhong‐Yuan

doi:10.1021/acs.jpclett.0c02960

Cited by 27 publications

(33 citation statements)

References 37 publications

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“…Therefore, to further improve their photocatalytic performance, developing an advanced method to realize highly efficient dissociation of excitons in polymeric semiconductors is urgently needed. However, most of the studies about polymeric photocatalysts are related to g-C 3 N 4 or conjugated polymers because of the lack of ordered structures in classical polymers. , In light of this, covalent organic frameworks (COFs), as a porous crystalline macromolecule with periodic and tailorable structures, can be ideal candidates to investigate excitonic effects by regulating their structures. − …”

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confidence: 99%

Boosting Reactive Oxygen Species Generation by Regulating Excitonic Effects in Porphyrinic Covalent Organic Frameworks

Wen

Gao

et al. 2022

J. Phys. Chem. Lett.

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Excitonic effects play a crucial role in determining the photocatalytic performance of polymer semiconductors, which has long been ignored. Herein, metal organic frameworks (MOFs, specially NH2-MIL-125) modifying porphyrinic covalent organic frameworks (COFs, specially DhaTph) have been proven to be a suitable model to regulate excitonic effects. The photoluminescence measurements prove that DhaTph presents strong excitonic effects, which can generate 1O2 through an energy transfer process. Remarkably, the construction of the NH2-MIL-125@DhaTph heterostructure can effectively facilitate the dissociation of excitons, resulting in distinct activation of O2 to O2 •– and •OH. Benefiting from the enhanced generation of reactive oxygen species, the NH2-MIL-125@DhaTph composite exhibits a superior bactericidal effect and photocatalytic degradation performance. This work provides a deeper insight into the excitonic effects based on COFs during the photocatalytic process and opens a feasible avenue for the regulation of the excitonic effects in porphyrinic COFs.

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confidence: 99%

Boosting Reactive Oxygen Species Generation by Regulating Excitonic Effects in Porphyrinic Covalent Organic Frameworks

Wen

Gao

et al. 2022

J. Phys. Chem. Lett.

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“…1,23 One theoretical study reported a difference in binding energy in different solvents, 107 which theoretically can lead to the growth of large single crystals. 188 But no direct origin for the obtained values could be found. 107 A more recent example is the ''ventilation vial'' approach to COF-300, using a cyclohexane and 1,4-dioxane mixture as reaction solvent.…”

Section: Interfacial Cof Growth and Solubility Dependencymentioning

confidence: 89%

Conquering the crystallinity conundrum: efforts to increase quality of covalent organic frameworks

et al. 2021

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“…The mechanisms for the kinetic products and the topology selection under different experimental conditions are still mysterious. Studies in the past have shown that the assembly pathways of monomers that are intrinsically related to reversible chemical reactions can determine the morphologies of products, such as single crystal, polycrystal, or crystallite. − Therefore, we employ molecular dynamics (MD) simulations to investigate the reaction-mediated assembly of monomers into isomers under different conditions. A general coarse-grained (CG) model is used for the monomer combination with [ C 2 + C 2 ] symmetry, whose unnecessary chemical details are ignored for computational acceleration.…”

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confidence: 99%

“…The CG interactions are set as short-range ones to have the same energy for two isomeric products. We use an Arrhenius two-state model to describe the reversible reactions . The influences of concentration, solvent condition, as well as the reversibility of chemical reactions are investigated in a wide parameter range.…”

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confidence: 99%

Mechanism for Topology Selection of Isomeric Two-Dimensional Covalent Organic Frameworks

Zhao

et al. 2022

J. Phys. Chem. Lett.

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The mechanism of growth of one of the competitive topologies for covalent organic frameworks with constitutional isomers is poorly understood. Herein, we employ molecular dynamics to study the isoenergetic assembly of the rhombic square (sql) and Kagome lattice (kgm). The concentration, solvent conditions, and the reversibility of chemical reactions are considered by means of an Arrhenius two-state model to describe the reactions. High concentrations and poor solvent both result in sql, agreeing well with recent experiments. Moreover, the high reversibility of reactions gives rise to sql, while the low reversibility leads to kgm, suggesting a new way of regulating the topology. Our analyses support that the nucleation of isomers influenced by experimental conditions is responsible for the selection of topologies, which improves understanding of the control of topology. We also propose a strategy in which a two-step growth can be exploited to greatly improve the crystallinity of kgm.

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Mechanisms of Defect Correction by Reversible Chemistries in Covalent Organic Frameworks

Cited by 27 publications

References 37 publications

Boosting Reactive Oxygen Species Generation by Regulating Excitonic Effects in Porphyrinic Covalent Organic Frameworks

Boosting Reactive Oxygen Species Generation by Regulating Excitonic Effects in Porphyrinic Covalent Organic Frameworks

Conquering the crystallinity conundrum: efforts to increase quality of covalent organic frameworks

Mechanism for Topology Selection of Isomeric Two-Dimensional Covalent Organic Frameworks

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