Precise Atomic Control of Adjacent Nitrogen Microenvironment in Covalent Organic Frameworks for Boosting Hydrogen Peroxide Photosynthesis DOI Creative Commons
Wei Zhou,

Wenjiao Wang,

Zhen Zhan

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 5, 2024

Abstract The microenvironmental changes on the skeleton of covalent organic frameworks (COFs) have an ineluctable impact photocatalytic performance. However, precise control at atomic level adjacent units and synergistic effect between imine bonds process are frequently overlooked. Herein, we develop various COFs with different nitrogen contents for (-C = N-) applied them to H2O2 photosynthesis. Distinct from traditional reactions, adsorption activation oxygen molecules may predominate over photogenerated charge migration in generation process. Specifically, -C N- atoms can more conducive lower reaction energy barrier, thereby facilitating reduction (ORR, O2 → 1O2 ●O2− H2O2). Notably, under AM 1.5G illumination, efficiency photosynthesis COF-T33 be up 88 mmol g− 1 h− 1, which is highest value reported so far similar conditions. Furthermore, only after 5 hours light irradiation, obtained content reach 0.44 wt%, meeting requirements industrial applications. This work deeply uncovers internal mechanism regulation microenvironment

Language: Английский

Three‐dimensional Covalent Organic Framework with Dense Lithiophilic Sites as Protective Layer to Enable High‐Performance Lithium Metal Battery DOI
Shuang Zheng, Yubin Fu,

Shuai Bi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 5, 2024

Lithium (Li) metal batteries with remarkable energy densities are restrained by short lifetime and low Coulombic efficiency (CE), resulting from the accumulative Li dendrites dead during cycling. Here, we prepared a new three-dimensional (3D) covalent organic framework (COF) dense lithiophilic sites (heteoatom weight contents of 32.32 wt %) as an anodic protective layer batteries. The 3D COF was synthesized using [6+4] synthesis strategy inducing flexible 6-connected cyclotriphosphazene derivative aldehyde 4-connected porphyrin-based tetraphenylamines. Both phosphazene porphyrin rings in served electron-rich sites, enhancing homogeneous

Language: Английский

Citations

13
Reticular Materials for Photocatalysis DOI
Kang Sun, Yunyang Qian, Dandan Li

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Abstract Photocatalysis leverages solar energy to overcome the thermodynamic barrier, enabling efficient chemical reactions under mild conditions. It can greatly reduce reliance on traditional sources and has attracted significant research interest. Reticular materials, including metal‐organic frameworks (MOFs) covalent organic (COFs), represent a class of crystalline materials constructed from molecular building blocks linked by coordination bonds, respectively. function as heterogeneous catalysts, combining well‐defined structures high tailorability akin homogeneous catalysts. In this review, regulation light absorption, charge separation, surface in photocatalytic process through precise molecular‐level design based features reticular is elaborated. Notably, for MOFsmicroenvironment modulation around catalytic sites affects performance delved, with emphasis their unique dynamic flexible microenvironments. For COFs, inherent excitonic effects due fully nature discussed highlight strategies regulate charge‐ and/or energy‐transfer‐mediated photocatalysis. Finally, current challenges future directions field, aiming provide comprehensive understanding how be optimized enhanced photocatalysis discussed.

Language: Английский

Citations

11
Exploring high-connectivity three-dimensional covalent organic frameworks: topologies, structures, and emerging applications DOI
Fengqian Chen,

Haorui Zheng,

Yusran Yusran

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

The design principles, development process, structural analysis, applications, challenges, and future directions of high-connectivity 3D COFs.

Language: Английский

Citations

10
Ethynyl‐Linked Donor–Acceptor Covalent Organic Framework for Highly Efficient Photocatalytic H2O2 Production DOI
Bowen Li, Jikun Chen, Kang Wang

et al.

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

Published: Jan. 19, 2025

Abstract Photocatalytic H 2 O synthesis from and is considered to be one of the most promising alternative approaches for manufacturing . Developing highly active selective photocatalysts significant in achieving efficient photosynthesis. Herein, an ethynyl‐linked donor–acceptor covalent organic framework (COF), named EBBT‐COF, prepared condensation reaction between electron‐deficient unit 4,4′,4″‐(1,3,5‐benzenetriyltri‐2,1‐ethynediyl)tris‐benzenamine electron‐rich benzo[1,2‐b:3,4‐b′:5,6‐b″]trithiophene‐2,5,8‐tricarboxaldehyde. Powder X‐ray diffraction N adsorption isotherm unveil crystalline porous hcb network EBBT‐COF with pores size centered at ca 2.3 nm. Spectroscopic characterizations demonstrate excellent visible‐light absorption capacity enhanced photo‐induced charge separation transport efficiency owing its architecture. Density functional theory calculations electrochemical tests indicate high activity selectivity toward 2e − reduction water oxidation triethynylbenzene trithiophene moieties accelerate ‐to‐H O‐to‐H conversion, respectively. These merits enable a photocatalyst generation yield rate 5 686 µmol g −1 h , optimal apparent quantum 15.14%, solar‐to‐chemical conversion 1.17% (λ > 400 nm), representing best performance among COF‐based reported thus far.

Language: Английский

Citations

2
Porphyrin‐Based Covalent Organic Frameworks for CO2 Photo/Electro‐Reduction DOI Open Access

Sun Tingting,

Zhi Wang, Yuhui Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 9, 2025

Photo/electro-catalytic CO2 reduction into high-value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post-modification capability, excellent stability, porphyrin-based covalent organic frameworks (COFs) have emerged as attractive photo/electro-catalysts towards reduction. In this review, the research progress of COFs photo/electro-catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Language: Английский

Citations

2
A Nanoporous Covalent Organic Framework Film-Based Optical Waveguide Sensor for H2S Gas Detection DOI
Patima Nizamidin,

Xiangdi Du,

Haiqi Gao

et al.

ACS Applied Nano Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

Language: Английский

Citations

1
10% Conversion of Imine into Thiazole in Covalent Organic Frameworks for Efficient Photocatalytic H2O2 Generation DOI Open Access

Xu Ding,

Tianying Wang, Baoqiu Yu

et al.

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

Published: March 17, 2025

Abstract The 5–10 nm exciton diffusion distance for most organic semiconductors is much less than the particle size of 2D covalent frameworks (COFs). As a result, local structure change in small domain COFs, rather whole particles, could effectively promote charge transfer photocatalysis. Herein, three‐component condensation used to preparing four mixed imine‐ and thiazole‐linked donor‐acceptor (D–A) COFs. In contrast 100% imine ca. 90% 10% materials have 77–95% higher photocatalytic hydrogen peroxide (H 2 O ) production rate pure water due more prolonged lifetime excitation state. particular, USTB‐10‐S exhibits H generation 5041 µmol g −1 h . Coupling with benzyl alcohol as sacrificial reagent, its further increased 16152 , superior COF‐based photocatalysts. This work illustrates proof‐of‐concept that COFs tiny amount able significantly enhance separation thus performance, inspiring development defect engineering field

Language: Английский

Citations

1
Unveiling the Impact of Microstructure Alterations on Photocatalytic Hydrogen Peroxide Preparation via DFT Prediction and Analysis DOI Creative Commons
Hong Tu, Zhichao Zhao,

Shunshun Chen

et al.

Energy & environment materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Photocatalytic technology has attracted much attention in the fields of clean energy and environmental governance. However, how to design develop highly efficient photocatalytic materials remains an urgent scientific problem be solved. This study focuses on enhancing activity through microstructure modification. Among them, ToRed‐4 showed most prominent performance. Under illumination condition 420 nm, its value was 13 506 μmol g −1 h , which approximately 18 times that CN550 (bulk g‐C 3 N 4 ) (719 ). By using DFT calculations, performance deeply analyzed, revealing significant advantages ToRed series key indicators underlying synergy mechanisms, including reduction HOMO‐LUMO gap, separation electron holes, expansion electronic transition range, transformation electrostatic potential distribution, increase dipole moment, optimization Coulomb attractive energy. The research results this provide a basis for opening up new avenues development are expected play important role related fields.

Language: Английский

Citations

1
Enhancing Donor–Acceptor Interaction and Framework Stability by the Povarov Reaction for Photocatalytic H2O2 Production DOI

Rui-Cheng Chen,

Can-Min Wu,

Lai‐Hon Chung

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 16, 2024

Language: Английский

Citations

5
Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO2 Cycloaddition DOI

Shengrong Yan,

Lan Zhang,

Songhu Shi

et al.

Chemical Research in Chinese Universities, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Language: Английский

Citations

0