Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D−π–A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation

JACS Au, Journal Year: 2023, Volume and Issue: 3(5), P. 1424 - 1434

Published: May 6, 2023

Simultaneously realizing efficient intramolecular charge transfer and mass transport in metal-free polymer photocatalysts is critical but challenging for environmental remediation. Herein, we develop a simple strategy to construct holey polymeric carbon nitride (PCN)-based donor-π-acceptor organic conjugated polymers via copolymerizing urea with 5-bromo-2-thiophenecarboxaldehyde (PCN-5B2T D-π-A OCPs). The resultant PCN-5B2T OCPs extended the π-conjugate structure introduced abundant micro-, meso-, macro-pores, which greatly promoted transfer, light absorption, thus significantly enhanced photocatalytic performance pollutant degradation. apparent rate constant of optimized OCP 2-mercaptobenzothiazole (2-MBT) removal ∼10 times higher than that pure PCN. Density functional theory calculations reveal photogenerated electrons are much easier from donor tertiary amine group benzene π-bridge then acceptor imine group, while 2-MBT more easily adsorbed on reacts holes. A Fukui function calculation intermediates predicted real-time changing actual reaction sites during entire degradation process. Additionally, computational fluid dynamics further verified rapid OCPs. These results demonstrate novel concept toward highly photocatalysis remediation by improving both transport.

Language: Английский

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Donor-acceptor-based conjugated polymers for photocatalytic energy conversion

EnergyChem, Journal Year: 2023, Volume and Issue: 6(1), P. 100116 - 100116

Published: Nov. 29, 2023

Language: Английский

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Oligo(phenylenevinylene)‐Based Covalent Organic Frameworks with Kagome Lattice for Boosting Photocatalytic Hydrogen Evolution

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: Oct. 2, 2023

Covalent organic frameworks (COFs) have shown great advantages as photocatalysts for hydrogen evolution. However, the effect of linkage geometry and type on extent π-electron conjugation in plane framework photocatalytic properties COFs remains a significant challenge. Herein, two Kagome (kgm) topologic oligo(phenylenevinylene)-based are designed synthesized boosting evolution via "two one" strategy. Under visible light irradiation, COF-954 with 5 wt% Pt cocatalyst exhibits high rate (HER) 137.23 mmol g

Language: Английский

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Molecular‐Level Regulation Strategies Toward Efficient Charge Separation in Donor−Acceptor Type Conjugated Polymers for Boosted Energy‐Related Photocatalysis

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(5)

Published: Dec. 11, 2023

Abstract The development of efficient photocatalysts for artificial photocatalytic energy conversion is an intriguing strategy. Promisingly, conjugated polymers (CPs) have been actively investigated as alternatives to traditional inorganic semiconductors photocatalysis due their molecularly tunable optoelectronic properties, thus providing a great platform molecular design. Incorporating donor (D) and acceptor (A) units into the backbone CPs ensures adequate D−A interface, which essential facilitating charge separation. This approach also allows bandgaps leading significant progress in conversions recent years. Here, fundamentals D–A type are initially outlined, followed by advanced experimental methods density functional theory (DFT) calculations investigating carrier dynamics. Then, detailed exposition synthetic strategies carried out. Their extensive applications diverse energy‐related conversions, such hydrogen evolution, oxygen overall water splitting, CO 2 reduction, N H O evolution comprehensively presented. review provides new comprehensive insights molecular‐level design catalysts boosted conversion, expected further advance photocatalysis.

Language: Английский

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S-Scheme Heterojunction/Single-Atom Dual-Driven Charge Transport for Photocatalytic Hydrogen Production

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7308 - 7320

Published: April 25, 2024

The rational design and modification of heterojunction photocatalysts aimed at achieving fast charge transport efficient photocatalytic performance is a central goal solar-light-driven water splitting hydrogen evolution, yet this remains challenge. Herein, we prepare hierarchical photocatalyst composed few-layer violet phosphorene (VP), cadmium sulfide (CdS) nanoparticles (NPs), Pd single atoms (SAs) by facile one-step ball-milling strategy. underlying VP/CdS p–n heterojunctions are verified to adopt S-scheme directional transfer combining in situ irradiated X-ray photoelectron spectroscopy electron paramagnetic resonance. atomically dispersed sites the low-valence state coupled with synergistically achieve ultrafast (2.2 ps), which interfacial Pd–S Pd–P bonds serve as channels. In addition, density-functional theory calculations reveal key role enhancement light-harvesting capacity optimization proton adsorption thermodynamics. A visible-light production rate 82.5 mmol h–1 g–1 attained an optimal 1 wt % Pd–5 photocatalyst, manifests 54-fold increase respect that CdS NPs, addition apparent quantum efficiency (AQE) 25.7% 420 nm. This work showcases valid combination SAs for separation promoting others.

Language: Английский

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Reticular design and alkyne bridge engineering in donor–π–acceptor type conjugated microporous polymers for boosting photocatalytic hydrogen evolution

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(13), P. 7693 - 7710

Published: Jan. 1, 2024

Through the successful application of Suzuki and Sonogashira coupling reactions, we have synthesized Py–TPA Py–TB–TPA CMPs, demonstrating impressive hydrogen evolution rates (HER) 3633 16 700 μmol g −1 h , respectively.

Language: Английский

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Self‐Floating Photocatalytic System for Highly Efficient Hydrogen Peroxide Production and Organic Synthesis on Carbon Dots Decorated Conjugated Microporous Polymer

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(28)

Published: Feb. 15, 2024

Abstract Photocatalytic oxygen (O 2 ) reduction to hydrogen peroxide (H O is considered be a promising method for energy storage. However, it suffers from the rapid recombination of carriers, limited solubility and slow diffusion , self‐decomposition H in traditional diphase systems. Here, self‐floating carbon dots/conjugated microporous polymer (CDs/CMP) photocatalytic system established production organic synthesis. Due D–π–A structure, porous hydrophobicity, CMP induced intramolecular charge transfer, exposed abundant reaction sites, enhanced adsorption. CDs act as “bridges” electron transmission regulate surface hydrophobicity CMP, further improving transfer optimizing interface. CDs/CMP exhibits high 8542.6 µmol g −1 h concurrent furoic acid at 2.22 m . This rate ≈90% higher than that system, exceeding all previously reported photocatalysts triphase Notably, achieves relative separation suppressing generated self‐decomposition. Theoretical calculations situ characterizations reveal mechanism evolution. provides insights into exploring application metal‐free heterogeneous reactions.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Sept. 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

Language: Английский

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Photocatalytic benzylamine coupling dominated by modulation of linkers in donor-acceptor covalent organic frameworks

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 352, P. 124020 - 124020

Published: April 21, 2024

Language: Английский

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Modulation of Schottky Barrier Height and Electronic Structure in Transition-Metal@Nitrogen-Doped-Carbon Core–Shell Cocatalysts Loaded with Mn_xCd_1–xS Nanorods for Enhanced Photocatalytic Hydrogen Evolution

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2315 - 2327

Published: Jan. 24, 2025

Language: Английский

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