Ethynyl‐Linked Donor–Acceptor Covalent Organic Framework for Highly Efficient Photocatalytic H₂O₂ Production

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

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Resorcinol‐Phthalaldehyde Resins for Photosynthesis of Hydrogen Peroxide: Modulation of Electronic Structure and Integration of Dual Channel Pathway

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(33)

Published: May 9, 2024

Abstract Modulating of electronic structure photocatalyst and integration dual channel pathway are promising strategy for efficient photosynthesis hydrogen peroxide (H 2 O ) from pure water without sacrificial agent oxygen exposure. In this work, nontoxic aromatic dialdehyde is used to replace the commonly toxic formaldehyde form resorcinol‐phthalaldehyde resins through a hydrothermal method. The introducing ring as π spacer increases separation distance electrons holes avoid their recombination. H can be produced via integrated reduction reaction (ORR) oxidation (WOR) due suitable energy band positions spatially separated sites. Resorcinol‐p‐phthalaldehyde (RP) resin exhibits yield 3351 µmol g −1 h with high apparent quantum (AQY) 14.9% at 420 nm solar‐to‐chemical conversion (SCC) efficiency 1.54%. This work provides simple modulate charge redox on molecular level design.

Language: Английский

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Ultrahigh photocatalytic hydrogen evolution of linear conjugated terpolymer enabled by an ultra-low ratio of benzothiadiazole monomer

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A terpolymer photocatalyst containing an ultra-low ratio of BT showed ultra-fast electron transfer and drastically lowered exciton binding energy, resulting in a hydrogen evolution rate up to 222.28 mmol h −1 g without the aid Pt co-catalysts.

Language: Английский

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Enhancing photocatalytic H2O2 production of donor−acceptor polymers by modulation of polymerization modes

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: unknown, P. 124856 - 124856

Published: Nov. 1, 2024

Language: Английский

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Donor–Acceptor-Conjugated Porous Polymer for Photopromoted N–H Formylation of Secondary Amines: Efficient In Situ N-Heterocyclic Carbene Catalysis in Radical Manner

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3889 - 3899

Published: Feb. 26, 2024

The photogenerated reactive oxygen species (ROSs) in N-heterocyclic carbene (NHC)-based heterogeneous photocatalysis hold promise for addressing the challenge of fostering Breslow-derived radicals. In this study, two conjugated porous polymers (CPPs), namely, Im-PCPP-1 and Im-PCPP-2, decorated with donor–acceptor-type porphyrin imidazole/imidazolium moieties, are synthesized via Suzuki–Miyaura coupling reaction. Importantly, ionization imidazole monomer effectively tunes push–pull effect D–A building blocks band structure Im-PCPPs. On basis, Im-PCPP-2 ionized imidazolium exhibits good catalytic activity toward oxidative N-formylation diverse secondary amines through cooperation photoredox situ NHC catalysis a radical manner, where acetaldehyde serves as carbon source formylation. Experimental calculation results suggest that multiple ROS play crucial roles: hydroxide OH– base to generate NHC; hydroxyl ·OH hydrogen atom transfer abstractors produce aza-Breslow-derived radicals partners cross-coupling; singlet 1O2 oxidant convert into cyclic peroxide. It is noteworthy photochemical process has achieved efficient conversion its derivatives high-value-added N-formamides.

Language: Английский

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Leveraging Phenazine and Dihydrophenazine Redox Dynamics in Conjugated Microporous Polymers for High-Efficiency Overall Photosynthesis of Hydrogen Peroxide

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 11972 - 11980

Published: Jan. 1, 2024

Leveraging the reversible phenazine–dihydrophenazine interconversion in microporous polymers enhances photocatalytic H 2 O generation by improving reduction and charge separation, showcasing a new approach for solar-driven chemical conversion.

Language: Английский

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Optimizing Adsorption‐Redox Sites and Charge Transfer of Ternary Polymer Photocatalyst with P─N Linkage for CO₂ Conversion Coupled with Antibiotics Removal

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

Published: June 3, 2024

Abstract The rational design of bifunctional photocatalysts with high adsorption and enrichment characteristics excellent photocatalytic redox activity is an effective way to address environmental pollution energy shortage crisis. In this study, cyclophosphazene‐derived porous organic polymer (PCPD) microspheres P─N linkage are coated graphene oxide (GO) loaded Ag 0 nanoparticles (NPs) prepare covalently bonded xAg‐rGO/PCPD composites. catalyst the highest specific surface area (denoted as 2.5Ag‐rGO/PCPD) shows capacity for fluoroquinolone antibiotics, removing 96.2% ciprofloxacin (CIP) through adsorption. By applying best 5Ag‐rGO/PCPD), 82.97% refractory sulfonamide antibiotics removed adsorption‐degradation, 635.3 µmol g −1 CO 162.3 CH 4 generated products 2 photoreduction alone. Among co‐catalytic systems, yield 9.16 obtained by coupling reduction levofloxacin (LVX) degradation harness electron‐donating power pollutant molecule. This study expected provide useful guidance photocatalysts.

Language: Английский

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Advancements in controlling COFs structure for enhanced crystallization properties and self-generated photocatalytic hydrogen peroxide

CrystEngComm, Journal Year: 2024, Volume and Issue: 26(24), P. 3143 - 3157

Published: Jan. 1, 2024

Highly crystalline COFs can improve the photocatalytic hydrogen peroxide yield.

Language: Английский

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Photo-enzyme cascade catalysis treatment of bisphenol A in water: Synergistic hydroxylation pathway for mineralization and detoxification

Journal of Hazardous Materials, Journal Year: 2025, Volume and Issue: 489, P. 137454 - 137454

Published: Jan. 31, 2025

Language: Английский

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Electro-Fenton process for wastewater treatment: From selective H2O2 generation to efficient •OH conversion

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160709 - 160709

Published: Feb. 1, 2025

Language: Английский

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