Facile Construction of Fully Conjugated Benzotristhiazole‐Based Covalent Organic Frameworks for Efficient Photocatalytic H2O2 Production DOI
Yuancheng Wang, Xin Zhao, Guangchao Han

et al.

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

Published: June 1, 2025

Abstract Vinylene‐linked covalent organic frameworks (COFs) have garnered significant attention owing to their extensive π‐electron delocalization and inherent stability. However, the synthesis difficulty lack of functional monomers available for Aldol reaction greatly restrict structural diversity application. Herein, a novel benzotristhiazole‐based monomer (BTZ) featuring rigid π‐conjugated structure is synthesized. Using this monomer, three highly crystalline vinylene‐linked COFs are successfully synthesized via trace solvent‐assisted strategy. Benefiting from stable N, S‐codoped conjugated structures, these exhibited excellent photocatalytic performance H 2 O generation. The incorporation triazine units found significantly improve activity, with styryl‐substituted unit demonstrating superior efficiency in promoting production compared phenyl‐substituted counterpart. Notably, BTZ‐3 exhibit hydrogen peroxide generation rate 3267 µmol h −1 g when benzyl alcohol (BA) employed as sacrificial agent. This research provides new synthetic strategy will facilitate diversities applications COFs.

Language: Английский

Coupling Ionic Polarization, Electron Sponge Effect by One‐Pot Hypercrosslinking, Pyridiniumnation of Photosensitizer‐Based Porous Organic Polymers for Enhancing Advanced Oxidation Process DOI

Wuzi Zhao,

Lixuan Kan,

Danfeng Wang

et al.

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

Published: April 4, 2025

Abstract Porous organic polymers (POPs) are emerging as up‐and‐coming photocatalysts for energy conversion, and environmental treatment. However, attention to simultaneously improving photoinduced charge separation, transfer, interfacial reaction is markedly lagged. Herein, the strategy of coupling ionic polarization, electron sponge effect enhancing built‐in electric field (BIEF), surface mass transfer process POPs proposed, which can be realized by a one‐pot post‐pyridiniumnation, Friedel‐Craft reaction. This method endows polarization elevating BIEF boosting separation/migration. The pyridiniumnation not only induces allow shallow trap free electrons but also effectively reduces oxygen adsorption energy, pertinent intermediates, thus leading stronger in 2.73‐fold neutral polymer strengthened O 2 activation. Additionally, photothermal performance with up 15 °C increment contributes enhancement photocatalysis. Consequently, iBPyP‐33 exhibits an unprecedentedly efficient photodegradation 100 ppm bisphenol A (BPA) just 20 min, photosynthesis H rate 3070 µmol g −1 h air, 6583 aided sodium ethylenediaminetetraacetic acid. study provides fresh, valuable insights into design high efficiency.

Language: Английский

Citations

0
Simultaneous High-Efficiency Photocatalytic Production of H2O2 and Synthesis of 3-HBA Using COFs Broadened by π Conjugate Networks and Photogenerated Charges DOI

Zeyu Sun,

Ling Li,

Shuyan Fan

et al.

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

Published: April 16, 2025

The coupling of H2O2 photosynthesis with photogenerated electrons and holes, when used separately, not only realizes the production value-added products but also maximizes energy utilization. However, achieving this remains a challenge. Here, we report three variations triazine-based covalent organic frameworks (COFs) featuring phenyl π-π-conjugated structures furthermore introduce phenoxy COF p-π-conjugated structure as control to effectively produce hydrogen peroxide. It is found that strong π-π conjugate network triggers pronounced optical response provides channels for charge transfer electron enrichment. results showed yield TTBA-TP-COF (TTBA = 4,4,4-(1,3,5-triazine-2,4,6-triyl) tris (([1,1-biphenyl]-4-amine)), TP 2,4,6-triformylphloroglucinol) reached an impressive 11,982 μmol/g/h, which was 1.49 times, 8.77 7.20 times TAPT-TP-COF (TAPT 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline), MA-TP-COF (MA melamine), TTTT-TP-COF (TTTT 4,4',4″-((1,3,5-triazine-2,4,6-triyl)tris(oxy))trianiline), respectively. Considering atomic economy, pioneeringly put forward strategy using holes separately. Concurrently, photocatalytic peroxide, acetaldehyde produced by hole oxidation, sacrificial ethanol served primary feedstock, aldol condensation successfully catalyzed 3-hydroxybutyraldehyde (3-HBA) under alkaline conditions provided small amount triethylamine. concentration 3-HBA confirmed be 23.84 mmol/L means mass spectrometry high-performance liquid chromatography.

Language: Английский

Citations

0
Encapsulation of Single‐Atoms into Covalent Organic Frameworks for Highly Efficient and Persistent H2O2 Photosynthesis via Biphasic Flow Chemistry DOI
Fang Lei, S. Qiu, Hui Xu

et al.

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

Published: April 16, 2025

Abstract Covalent organic frameworks (COFs) metallization offers a potent protocol for augmenting the efficacy of artificial photosynthesis H 2 O . However, hurdles like intractable short exciton lifetime and precarious metal coordination metallo‐COFs impede their photocatalytic proficiency. Herein, facile universal single‐atom encapsulation strategy is proposed, through which Fe atoms are precisely anchored in pincer structure to achieve planar locking PP‐COF enhance its π‐conjugation effect. The Fe/PP‐COF with extremely high stability exhibits remarkable migration distance (6.48–53.20 nm) (296.75 ps), representing state‐of‐the‐art COF hitherto. In brand‐new biphasic flow reactor, within 60 h reaction allows continuous at rate 1556 µmol −1 an unprecedented concentration 100 m , no leakage. This work valuable insights into developing COFs precise regulation single‐atoms space‐time production.

Language: Английский

Citations

0
Facile Construction of Fully Conjugated Benzotristhiazole‐Based Covalent Organic Frameworks for Efficient Photocatalytic H2O2 Production DOI
Yuancheng Wang, Xin Zhao, Guangchao Han

et al.

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

Published: June 1, 2025

Abstract Vinylene‐linked covalent organic frameworks (COFs) have garnered significant attention owing to their extensive π‐electron delocalization and inherent stability. However, the synthesis difficulty lack of functional monomers available for Aldol reaction greatly restrict structural diversity application. Herein, a novel benzotristhiazole‐based monomer (BTZ) featuring rigid π‐conjugated structure is synthesized. Using this monomer, three highly crystalline vinylene‐linked COFs are successfully synthesized via trace solvent‐assisted strategy. Benefiting from stable N, S‐codoped conjugated structures, these exhibited excellent photocatalytic performance H 2 O generation. The incorporation triazine units found significantly improve activity, with styryl‐substituted unit demonstrating superior efficiency in promoting production compared phenyl‐substituted counterpart. Notably, BTZ‐3 exhibit hydrogen peroxide generation rate 3267 µmol h −1 g when benzyl alcohol (BA) employed as sacrificial agent. This research provides new synthetic strategy will facilitate diversities applications COFs.

Language: Английский

Citations

0