Linker Length Engineering toward Enhanced Photocatalytic Aerobic Oxidation in Benzothiadiazole-Based Covalent Organic Frameworks DOI

Chao‐Qin Han,

Zeyang Wang, Shuai Sun

et al.

ACS Materials Letters, Journal Year: 2024, Volume and Issue: unknown, P. 393 - 400

Published: Dec. 26, 2024

The intrinsic structural advantages and tunability of covalent organic frameworks (COFs) have made them promising photocatalysts for various photocatalytic reactions. However, it remains a great challenge to systematically tune the linker lengths build linker-length-dependent structure-performance relationship COFs-based photocatalysts. Herein, five isoreticular COFs with sql underlying nets been successfully synthesized using benzothiadiazole-based ditopic aldehydes varied 1,3,6,8-tetrakis(4-aminophenyl)pyrene as building units. obtained exhibit significantly different activities toward aerobic oxidation. Remarkably, COF-containing vinyl group, HIAM-0020, exhibited best performance near-unity conversion selectivity oxidative benzylamine coupling within 2 h. experimental theoretical investigations indicate that HIAM-0020 exhibits faster charge separation ability lower migration resistance compared other four COFs. This work represents guidance rational design synthesis COF-based achieve efficient transformation.

Language: Английский

Dual‐Functional Benzotrithiophene‐Based Covalent Organic Frameworks for Photocatalytic Detoxification of Mustard Gas Simulants and Antibacterial Defense DOI Open Access

Yongchao Zhu,

Liyang Qin,

Mingyuan Yang

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Abstract The persistent threats posed by toxic chemical warfare agents (CWAs) such as mustard gas (bis(2‐chloroethyl) sulfide, HD) and bacterial contaminants demand the development of innovative, sustainable mitigation strategies. Photocatalytic processes that generate reactive oxygen species (ROS) offer a promising dual‐functional approach for both detoxification antibacterial defense. In this study, two structurally analogous covalent organic frameworks (COFs), BPY‐COF BD‐COF, are synthesized using benzotrithiophene donor unit paired with bipyridine biphenyl, respectively. These COFs exhibit high crystallinity, broad‐spectrum light absorption, efficient charge carrier transport, demonstrating superior performance due to incorporation heteroatoms. achieved ultrafast simulant 2‐chloroethyl ethyl sulfide (CEES) half‐life 35 min 100% selectivity sulfoxide (CEESO) under white LED light, outperforming BD‐COF. Additionally, electrospun composite fibers containing 40 wt.% maintained comparable CEES degradation rates exhibited over 99% efficiency against Escherichia coli Bacillus subtilis within 60 min. findings highlight potential multifunctional photocatalyst integrated applications in defense, addressing critical challenges public health safety.

Language: Английский

Citations

1
Enhanced Photocatalytic Production of Hydrogen Peroxide by Covalent Triazine Frameworks with Stepwise Electron Transfer DOI
Hao Zhang, Wenxin Wei, Kai Chi

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17654 - 17663

Published: Nov. 15, 2024

The photosynthesis of hydrogen peroxide (H2O2) from pure water and oxygen using metal-free photocatalysts offers a renewable approach to convert solar energy storable chemical energy. However, the efficiency H2O2 is often hindered by rapid recombination photogenerated charge carriers. Herein, we present an elegantly designed covalent triazine framework (CTF) photocatalyst, denoted as Ace-asy-CTF, with stepwise electron transfer pathway for highly efficient H2O2. Notably, Ace-asy-CTF possesses localized excited-state distribution that created weakly conjugated acetenyl units in asymmetric frameworks, revealed transient spectroscopies further supported theoretical calculations. Meanwhile, introduced also serve active sites reduction reaction (ORR). simultaneously enhanced two-step 2e– ORR result excellent yield 2594 μmol g–1 h–1, directly produced without requiring any sacrificial reagents. This work paves way development next-generation catalysts, providing feasible benchmark stable

Language: Английский

Citations

8
Enhancing Electron Donor–Acceptor Complex Photoactivation with a Stable Perylene Diimide Metal–Organic Framework DOI Creative Commons
Xia Wu, Ming Cui, Kun Wu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Electron donor–acceptor complexes are commonly employed to facilitate photoinduced radical-mediated organic reactions. However, achieving these photochemical processes with catalytic amounts of donors or acceptors can be challenging, especially when aiming reduce catalyst loadings. Herein, we have unveiled a framework-based heterogenization approach that significantly enhances the photoredox activity perylene diimide species in radical addition reactions alkyl silicates by promoting faster and more efficient electron complex formation. Besides offering broad substrate scope alkene hydroalkylation, newly developed heterogeneous photocatalysis substantially improves turnover numbers comparison previous homogeneous photocatalytic systems demonstrates outstanding recyclability. These research findings pave way for advancement various practical transformations using framework-supported organocatalysts.

Language: Английский

Citations

0
Enhanced efficiency and selectivity in reactive oxygen species generation using thiazolo[5,4-d]thiazole-based supramolecular photosensitizers DOI
Guang Wang,

Tongfei Qi,

Xianjun Yin

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Language: Английский

Citations

0
A double-walled porous metal-perylenediimide framework for enhanced photocatalysis DOI
Lili Ma,

Feinian Yang,

Longyi Ding

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Language: Английский

Citations

0
Covalent organic frameworks for enhanced photocatalytic extraction of uranium via the modulation of charge transfer pathways DOI
Chang Liu, Yaoxuan Wang,

Zhimin Dong

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 163078 - 163078

Published: April 1, 2025

Language: Английский

Citations

0
Linker Length Engineering toward Enhanced Photocatalytic Aerobic Oxidation in Benzothiadiazole-Based Covalent Organic Frameworks DOI

Chao‐Qin Han,

Zeyang Wang, Shuai Sun

et al.

ACS Materials Letters, Journal Year: 2024, Volume and Issue: unknown, P. 393 - 400

Published: Dec. 26, 2024

The intrinsic structural advantages and tunability of covalent organic frameworks (COFs) have made them promising photocatalysts for various photocatalytic reactions. However, it remains a great challenge to systematically tune the linker lengths build linker-length-dependent structure-performance relationship COFs-based photocatalysts. Herein, five isoreticular COFs with sql underlying nets been successfully synthesized using benzothiadiazole-based ditopic aldehydes varied 1,3,6,8-tetrakis(4-aminophenyl)pyrene as building units. obtained exhibit significantly different activities toward aerobic oxidation. Remarkably, COF-containing vinyl group, HIAM-0020, exhibited best performance near-unity conversion selectivity oxidative benzylamine coupling within 2 h. experimental theoretical investigations indicate that HIAM-0020 exhibits faster charge separation ability lower migration resistance compared other four COFs. This work represents guidance rational design synthesis COF-based achieve efficient transformation.

Language: Английский

Citations

1