Pyridyl‐Imine‐Functionalized Donor–Acceptor Covalent Organic Frameworks for Optimal Photosynthesis of Hydrogen Peroxide DOI Open Access
Zixuan Li,

Bingzi Cai,

Ying Zou

et al.

Advanced Energy Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Abstract The artificial photosynthesis of hydrogen peroxide (H 2 O ) using semiconductor photocatalysts is gaining attention as an eco‐friendly and energy‐efficient method. Covalent organic frameworks (COFs) show great promise in enhancing photocatalytic H production due to their tunable structures functional diversity. However, the efficiency generation close photoelectric properties COFs microenvironment active sites. Herein, synthesis pyridyl‐imine‐functionalized (PyIm‐COFs) featuring donor–acceptor (D–A) moieties improve reported. By employing benzothiadiazole (BT) units with varied fluorine substitutions, electronic environment sites, optimizing selective two‐electron (2e − oxygen reduction reaction (ORR), tuned. Among synthesized COFs, PyIm‐BT_F exhibits highest activity, achieving a rate 5342 µmol g −1 h . importance D–A rational design COF‐based photocatalysts, providing novel strategy for sustainable through optimized site environments, underscored.

Language: Английский

Construction of Crystalline Nitrone-Linked Covalent Organic Frameworks Via Kröhnke Oxidation DOI
Fangyuan Kang, Xin Wang, Cailing Chen

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15465 - 15472

Published: July 7, 2023

Developing diverse synthetic routes to prepare various crystalline covalent organic frameworks (COFs) and enrich the family of COFs is very important highly desirable. In this research, we demonstrate that Kröhnke oxidation (originally developed carbonyl compounds) can be employed as an efficient method construct two nitrone-linked (CityU-1 CityU-2) through ingenious design polynitroso-containing precursors well exquisite control polymerization conditions. The formation structure nitrone-based linkage units have been confirmed a mode reaction. as-obtained characterized by Fourier transform infrared X-ray photoelectron spectroscopy, powder diffraction patterns, scanning electron microscopy. Notably, CityU-1 exhibits BET specific surface area 497.9 m2g-1 with I2 capture capacity 3.0 g g-1 at 75 °C. Our research would provide more chances for applications.

Language: Английский

Citations

86
Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction DOI

Guang-Bo Wang,

Yanjing Wang, Jing‐Lan Kan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4951 - 4956

Published: Feb. 27, 2023

Multicomponent reactions (MCRs), as a powerful one-pot combinatorial synthesis tool, have been recently applied to the of covalent organic frameworks (COFs). Compared with thermally driven MCRs, photocatalytic MCR-based COF has not yet investigated. Herein, we first report construction COFs by multicomponent reaction. Upon visible-light irradiation, series excellent crystallinity, stability, and permanent porosity are successfully synthesized via photoredox-catalyzed Petasis reaction under ambient conditions. Additionally, obtained Cy-N3-COF exhibits photoactivity recyclability for visible-light-driven oxidative hydroxylation arylboronic acids. The concept polymerization only enriches methodology but also opens new avenue that might be possible existing synthetic methods based on MCRs.

Language: Английский

Citations

73
Covalent organic frameworks in heterogeneous catalysis: recent advances and future perspective DOI
Ziad Alsudairy,

Normanda Brown,

Allea Campbell

et al.

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(16), P. 3298 - 3331

Published: Jan. 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.

Language: Английский

Citations

64
Boosting CO2 Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework DOI
Lei Zou, Ziao Chen, Duan‐Hui Si

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 28, 2023

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through construction one-dimensional (1D) pyrene-based (PyTTA-COF). The dual-chain-like edge architectures 1D PyTTA-COF enable stabilization aromatic backbones, thus reducing loss during exciton dissociation and thermal relaxation, which provides energetic to traverse linkages. As result, exhibits significantly enhanced photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding remarkable CO evolution 1003 μmol g-1 over an 8-hour period, surpasses that corresponding 2D counterpart by factor 59. These findings valuable approach address charge limitations COFs.

Language: Английский

Citations

54
Pore Space Partition Synthetic Strategy in Imine-linked Multivariate Covalent Organic Frameworks DOI
Mengjie Hao,

Yinghui Xie,

Ming Lei

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(3), P. 1904 - 1913

Published: Dec. 22, 2023

Partitioning the pores of covalent organic frameworks (COFs) is an attractive strategy for introducing microporosity and achieving new functionality, but it technically challenging to achieve. Herein, we report a simple partitioning micropores/mesopores multivariate COFs. Our approach relies on predesign synthesis multicomponent COFs through imine condensation reactions with aldehyde groups anchored in COF pores, followed by inserting additional symmetric building blocks (with C2 or C3 symmetries) as pore partition agents. This allowed tetragonal hexagonal be partitioned into two three smaller micropores, respectively. The synthesized library pore-partitioned was then applied capture iodine pollutants (i.e., I2 CH3I). rich inventory deep exploration relationships between adsorbent composition, architecture, adsorption capacity CH3I under wide-ranging conditions. Notably, one our developed (COF 3-2P) exhibited greatly enhanced dynamic performances compared its parent 3) breakthrough tests, setting benchmark COF-based adsorbents. Results present effective design toward functional tunable environments, functions, properties.

Language: Английский

Citations

50
Single-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis DOI Creative Commons
Ziqi Zhang, Zhe Zhang, Cailing Chen

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 22, 2024

Abstract Two-dimensional (2D) covalent organic frameworks (COFs) and their derivatives have been widely applied as electrocatalysts owing to unique nanoscale pore configurations, stable periodic structures, abundant coordination sites high surface area. This work aims construct a non-thermodynamically Pt-N 2 active site by electrochemically modifying platinum (Pt) single atoms into fully conjugated 2D COF conductive agent-free pyrolysis-free electrocatalyst for the hydrogen evolution reaction (HER). In addition maximizing atomic utilization, single-atom catalysts with definite structures can be used investigate catalytic mechanisms structure-activity relationships. this work, in-situ characterizations theoretical calculations reveal that nitrogen-rich graphene analogue not only exhibits favorable metal-support effect Pt, adjusting binding energy between Pt H* intermediates forming instead of typical 4 environment, but also enhances electron transport ability structural stability, showing both conductivity stability in acidic environments.

Language: Английский

Citations

42
Covalent Organic Framework Nanoarchitectonics: Recent Advances for Precious Metal Recovery DOI Creative Commons

Weikang Guo,

Jiale Liu,

Haijuan Tao

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(33)

Published: June 19, 2024

The recovery of precious metals (PMs) from secondary resources has garnered significant attention due to environmental and economic considerations. Covalent organic frameworks (COFs) have emerged as promising adsorbents for this purpose, owing their tunable pore size, facile functionalization, exceptional chemical stability, large specific surface area. This review provides an overview the latest research progress in utilizing COFs recover PMs. Firstly, design synthesis strategies chemically stable COF-based materials, including pristine COFs, functionalized composites, are delineated. Furthermore, application gold, silver, platinum group elements is delved into, emphasizing high adsorption capacity selectivity well recycling ability. Additionally, various interaction mechanisms between PM ions analyzed. Finally, current challenges faced by field discussed, potential directions future development proposed, enhancing recyclability reusability COF materials realizing PMs actual acidic wastewater. With targeted can be realized more economically efficiently future.

Language: Английский

Citations

33
A durable hydrophobicity hydrazone covalent organic framework coating for solid phase microextraction of polycyclic aromatic hydrocarbons in food and environmental sample DOI
Shuhui Huo, Xiaohui Deng, Nan Yang

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 481, P. 148562 - 148562

Published: Jan. 4, 2024

Language: Английский

Citations

24
Highly Conductive Imidazolate Covalent Organic Frameworks with Ether Chains as Solid Electrolytes for Lithium Metal Batteries DOI Creative Commons
Yufei Yuan, Zeyu Zhang, Zhengyang Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 20, 2024

Abstract Poly(ethylene oxide) (PEO)‐based electrolytes are often used for Li + conduction as they can dissociate the salts efficiently. However, high entanglement of chains and lack pathways rapid ion diffusion limit their applications in advanced batteries. Recent developments ionic covalent organic frameworks (iCOFs) showed that highly ordered structures provide efficient transport, solving limitations traditional PEO‐based electrolytes. Here, we present imidazolate COFs, PI‐TMEFB‐COFs, having methoxyethoxy chains, synthesized by Debus–Radziszewski multicomponent reactions ionized form, @PI‐TMEFB‐COFs, showing a conductivity 8.81 mS cm −1 transference number 0.974. The mechanism such excellent electrochemical properties is LiClO 4 , making free then those transported through COFs’ pores. @PI‐TMEFB‐COFs formed stable interface with metal. Thus, employing solid electrolyte to assemble LiFePO batteries an initial discharge capacity 119.2 mAh g at 0.5 C, 82.0 % 99.9 Coulombic efficiency were maintained after 400 cycles. These results show iCOFs ether via create new chapter rechargeable

Language: Английский

Citations

19
COFs‐Based Metal‐Free Heterojunctions for Solar‐to‐Chemical Energy Conversion DOI
Tianyu Zhou, Yunchao Ma, Hao Feng

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(49)

Published: Aug. 17, 2024

Abstract Covalent organic frameworks (COFs) are a promising class of polymers with the merits robust framework, ultrahigh porosity, and molecularly precise backbones, which reveals great potential for solar‐to‐chemical energy conversion in context mitigating environmental crises. However, photochemical activities individual COFs not as desired, primarily due to their limited light absorption, insufficient dissociation photogenerated excitons readily recombined carriers. Recently, COFs‐based metal‐free heterojunctions synergistic effects provide feasible route boost photocatalytic activity more environmentally friendly cost‐competitive manners. Herein, it is first systematically overview advances from heterojunction types, heterointerfaces interactions, primary design mechanisms. Then, typical photocatalysts (e.g., g‐C 3 N 4 ‐COFs, carbon materials‐COFs, polymer semiconductor‐COFs, COFs‐COFs heterojunction) summarized. Finally, challenges long‐term outlooks future offered terms efficiency, yield, stability, cost reaction mechanisms, well standardized evaluation method activities. It anticipated that this review can deliver new insights into fundamental engineering conversion, further accelerate development area.

Language: Английский

Citations

18