Vinylene‐linked Donor‐π‐Acceptor Metal‐Covalent Organic Framework for Enhanced Photocatalytic CO2 Reduction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)

Опубликована: Сен. 3, 2024

Abstract Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal‐covalent organic framework (MCOF) based photocatalyst. However, robust achieving both simultaneously has yet to be challenging despite ongoing efforts. Here we develop a fully π‐conjugated vinylene‐linked multivariate donor‐π‐acceptor MCOF (D‐π‐A, termed UJN‐1) by integrating benzyl cyanides linker with multiple functional electron‐rich triphenylamine electron‐deficient copper‐cyclic trinuclear units (Cu‐CTUs) moieties, featuring strong intramolecular force, extended conjugation degree skeleton, abundant active sites. The incorporation Cu‐CTUs acceptor electron‐withdrawing ability concomitantly giant can efficiently accelerate photogenerated electrons transfer from Cu‐CTUs, revealing experiments theoretical calculations. Benefiting synergistically effect D‐π‐A configuration vinylene linkage, highly‐efficient spatial is achieved. Consequently, UJN‐1 exhibits an excellent CO formation rate 114.8 μmol g −1 in 4 h without any co‐catalysts or sacrificial reagents under visible light, outperforming those analogous MCOFs imine‐linked (UJN‐2, 28.9 ) COF Cu‐CTU sites (UJN‐3, 50.0 ), emphasizing role designing novel COFs‐based

Язык: Английский

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Expanding Olefin-Linked Covalent Organic Frameworks toward Selective Photocatalytic Oxidation of Organic Sulfides

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(7), С. 8772 - 8782

Опубликована: Фев. 7, 2024

Olefin-linked covalent organic frameworks (COFs) have exhibited great potential in visible-light photocatalysis. In principle, expanding fully conjugated COFs can facilitate light absorption and charge transfer, leading to improved Herein, three olefin-linked with the same topology are synthesized by combining 2,4,6-trimethyl-1,3,5-triazine (TMT) 1,3,5-triformylbenzene (TFB), 1,3,5-tris(4-formylphenyl)benzene (TFPB), 1,3,5-tris(4-formylphenylethynyl)benzene (TFPEB), namely, TMT-TFB-COF, TMT-TFPB-COF, TMT-TFPEB-COF, respectively. From TMT-TFB-COF phenyl rings provides only limited expansion for π-conjugation due steric effect of structural twisting. However, from TMT-TFPB-COF insertion acetylenes eliminates more delocalized π-electrons. As such, TMT-TFPEB-COF exhibits best optoelectronic properties among these COFs. Consequently, photocatalytic performance is much better than those on oxidation sulfides into sulfoxides oxygen. The desirable reusability substrate compatibility photocatalyst further confirmed. selective formation over under blue irradiation proceeds via both electron- energy-transfer pathways. This work highlights a rational design toward

Язык: Английский

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Functionality Modulation Toward Thianthrene‐based Metal‐Free Electrocatalysts for Water Splitting

Advanced Materials, Год журнала: 2024, Номер 36(18)

Опубликована: Янв. 21, 2024

The development of metal-free bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER OER) is significant but rarely demonstrated. Porous organic polymers (POPs) with well-defined electroactive functionalities show superior performance in reaction (HER) (OER). Precise control the active sites' local environment requires careful modulation linkers through judicious selection building units. Here, a systematic strategy introduced modulating functionality to design synthesize series thianthrene-based sp

Язык: Английский

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Material challenges in green hydrogen ecosystem

Coordination Chemistry Reviews, Год журнала: 2023, Номер 494, С. 215272 - 215272

Опубликована: Июль 17, 2023

Язык: Английский

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Rational design of D− π − A− π − D porous organic polymer with polarized π for photocatalytic aerobic oxidation

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 334, С. 122847 - 122847

Опубликована: Май 4, 2023

Язык: Английский

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