Post-synthetic modification of covalent organic frameworks for CO2 electroreduction

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

Опубликована: Июнь 26, 2023

To achieve high-efficiency catalysts for CO2 reduction reaction, various catalytic metal centres and linker molecules have been assembled into covalent organic frameworks. The amine-linkages enhance the binding ability of molecules, ionic frameworks enable to improve electronic conductivity charge transfer along However, directly synthesis with is hardly achieved due electrostatic repulsion predicament strength linkage. Herein, we demonstrate reaction by modulating linkers linkages template framework build correlation between performance structures Through double modifications, states are well tuned, resulting in controllable activity selectivity reaction. Notably, dual-functional achieves high a maximum CO Faradaic efficiency 97.32% turnover frequencies value 9922.68 h-1, which higher than those base single-modified Moreover, theoretical calculations further reveal that attributed easier formation immediate *CO from COOH*. This study provides insights developing

Язык: Английский

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One‐Dimensional Covalent Organic Frameworks for the 2e⁻ Oxygen Reduction Reaction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Янв. 19, 2023

Two-dimensional covalent organic frameworks (2D COFs) are often employed for electrocatalytic systems because of their structural diversity. However, the efficiency atom utilization is still in need improvement, catalytic centers located basal layers and it difficult electrolytes to access them. Herein, we demonstrate use 1D COFs 2e- oxygen reduction reaction (ORR). The different four-connectivity blocks resulted prepared displaying good crystallinity, high surface areas, excellent chemical stability. more exposed sites showing large electrochemically active 4.8-fold that a control 2D COF, thus enabled catalysis ORR with higher H2 O2 selectivity 85.8 % activity, TOF value 0.051 s-1 at 0.2 V, than COF (72.9 0.032 ). This work paves way development low dimensions electrocatalysis.

Язык: Английский

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Dithiine-linked metalphthalocyanine framework with undulated layers for highly efficient and stable H2O2 electroproduction

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Янв. 23, 2024

Realization of stable and industrial-level H

Язык: Английский

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Advances in COFs for energy storage devices: Harnessing the potential of covalent organic framework materials

Energy storage materials, Год журнала: 2023, Номер 63, С. 103014 - 103014

Опубликована: Окт. 7, 2023

Язык: Английский

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Regulated High‐Spin State and Constrained Charge Behavior of Active Cobalt Sites in Covalent Organic Frameworks for Promoting Electrocatalytic Oxygen Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 3, 2023

A novel type of covalent organic frameworks has been developed by assembling definite cobalt-nitrogen-carbon configurations onto carbon nanotubes using linkers that have varying electronic effects. This innovative approach resulted in an efficient electrocatalyst for oxygen reduction, which is understood a combination situ spectroelectrochemistry and the bond order theorem. The strong interaction between electron-donating electron-accepting linker mitigates trend charge loss at cobalt sites, while inducing generation high spin state. enhances adsorption strength electron transfer center reactants/intermediates, leading to improved reduction capability. work not only presents effective strategy developing non-noble metal electrocatalysts through reticular chemistry, but also provides valuable insights into regulating configuration behavior active sites designing high-performance electrocatalysts.

Язык: Английский

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New Advances in Covalent Network Polymers via Dynamic Covalent Chemistry

Chemical Reviews, Год журнала: 2024, Номер 124(12), С. 7829 - 7906

Опубликована: Июнь 3, 2024

Covalent network polymers, as materials composed of atoms interconnected by covalent bonds in a continuous network, are known for their thermal and chemical stability. Over the past two decades, these have undergone significant transformations, gaining properties such malleability, environmental responsiveness, recyclability, crystallinity, customizable porosity, enabled development integration dynamic chemistry (DCvC). In this review, we explore innovative realm polymers focusing on recent advances achieved through application DCvC. We start examining history fundamental principles DCvC, detailing its inception core concepts noting key role reversible bond formation. Then reprocessability DCvC is thoroughly discussed, starting from milestones that marked evolution progressing to current trends applications. The influence crystallinity then reviewed, covering diversity, synthesis techniques, functionalities. concluding section, address challenges faced field speculates potential future directions.

Язык: Английский

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Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for Efficient Oxygen Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(39)

Опубликована: Июль 24, 2023

The atom-cluster interaction has recently been exploited as an effective way to increase the performance of metal-nitrogen-carbon catalysts for oxygen reduction reaction (ORR). However, rational design such and understanding their structure-property correlations remain a great challenge. Herein, we demonstrate that introduction adjacent metal (M)-N4 single atoms (SAs) could significantly improve ORR well-screened Fe atomic cluster (AC) catalyst by combining density functional theory (DFT) calculations experimental analysis. DFT studies suggest Cu-N4 SAs act modulator assist O2 adsorption cleavage O-O bond on AC active center, well optimize release OH* intermediates accelerate whole kinetic. depositing with nitrogen doped mesoporous carbon nanosheet are then constructed through universal interfacial monomicelles assembly strategy. Consistent theoretical predictions, resultant exhibits outstanding half-wave potential 0.92 eV in alkali 0.80 acid, high power 214.8 mW cm-2 zinc air battery. This work provides novel strategy precisely tuning atomically dispersed poly-metallic centers electrocatalysis.

Язык: Английский

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Optimization Strategies of Covalent Organic Frameworks and Their Derivatives for Electrocatalytic Applications

Advanced Functional Materials, Год журнала: 2023, Номер 34(11)

Опубликована: Ноя. 27, 2023

Abstract Covalent organic frameworks (COFs) are crystalline porous polymers that can be precisely integrated by building blocks to achieve pre‐designed composition, components, and functions, making them a powerful platform for the development of molecular devices in field electrocatalysis. The precise control channel/dopant positions highly ordered network structures COFs provide an ideal material system applications advanced In this paper, topological structure design synthesis methods reviewed detail, their principles deeply analyzed. addition, derivatives electrocatalysis systematically summarized optimization strategies proposed. Finally, application prospects challenges may encountered future prospected, providing helpful guidance research.

Язык: Английский

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Non‐Interpenetrated 3D Covalent Organic Framework with Dia Topology for Au Ions Capture

Advanced Functional Materials, Год журнала: 2023, Номер 33(33)

Опубликована: Апрель 23, 2023

Abstract The 3D covalent organic frameworks (COFs) have attracted considerable attention owing to their unique structural characteristics. However, most of COFs interpenetration phenomena, which will result in decreased surface area and porosities, thus limited applications molecular/gas capture. Developing with non‐fold is challenging but significant because the existence non‐covalent interactions between adjacent nets. Herein, a new COF (BMTA‐TFPM‐COF) dia topology for Au ion capture first demonstrated. constructed exhibits high Brunauer–Emmett–Teller 1924 m 2 g −1 , pore volume 1.85 cm 3 . abundant cavities as well exposed CN linkages due non‐interpenetration enable absorb 3+ capacity (570.18 mg ), selectivity (99.5%), efficiency (68.3% adsorption maximum 5 min). This work provides strategy design

Язык: Английский

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Catalytic Linkage Engineering of Covalent Organic Frameworks for the Oxygen Reduction Reaction

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

Опубликована: Апрель 28, 2023

Metal-free covalent organic frameworks (COFs) have been employed to catalyze the oxygen reduction reaction (ORR). To achieve high activity and selectivity, various building blocks containing heteroatoms groups linked by imine bonds were used create catalytic COFs. However, roles of linkages COFs in ORR not investigated. In this work, linkage engineering has modulate behaviors. single sites while avoiding other possible sites, we synthesized from benzene units bonds, such as imine, amide, azine, oxazole bonds. Among these COFs, oxazole-linkage enables with highest activity, which achieved a half-wave potential 0.75 V limited current density 5.5 mA cm-2 . Moreover, oxazole-linked COF conversion frequency (TOF) value 0.0133 S-1 , 1.9, 1.3, 7.4-times that azine-, amide- imine-COFs, respectively. The theoretical calculation showed carbon atoms facilitated formation OOH* promoted protonation O* form OH*, thus advancing activity. This work guides us on are suitable for ORR.

Язык: Английский

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