Photocatalytic Hydrogen Production on a sp²‐Carbon‐Linked Covalent Organic Framework

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Aug. 27, 2022

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have emerged as attractive platforms for solar‐to‐chemical energy conversion. In this study, we implemented a gradient heating strategy to synthesize sp 2 ‐carbon‐linked triazine‐based COF, COF‐JLU100, exhibiting high crystallinity, large surface area, good durability and carrier mobility solar‐driven photocatalytic hydrogen evolution. The Pt‐doped COF‐JLU100 demonstrated evolution rate of over 100 000 μmol g −1 h water splitting under visible‐light illumination (λ>420 nm). Experimental theoretical studies corroborate that the cyano‐vinylene segments in extend π‐delocalization enable fast charge transfer separation rates well dispersion water. Moreover, can be prepared by low‐cost easily available monomers has excellent stability, which is desirable practical production.

Language: Английский

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Reaction Pathways toward Sustainable Photosynthesis of Hydrogen Peroxide by Polymer Photocatalysts

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(10), P. 4259 - 4273

Published: May 11, 2022

Harnessing solar energy to generate hydrogen peroxide (H2O2) from H2O and O2 via artificial photosynthesis is an attractive route, as this approach only uses sunlight the input. Organic polymers have emerged a promising class of materials for solar-driven H2O2 production, owing their virtually unlimited molecular building blocks rich bond-forming reactions. This distinctive feature leads existence different reaction pathways characterized by electron transfer numbers. For overall H2O2, reduction oxidation must occur concurrently. Thus, in-depth insights into these are crucial with eventual aim steering optimize efficiency. In perspective, we primarily focus on state-of-the-art progress in developing polymer photocatalysts coupling We also present key challenges opportunities production future. offer ample molecular-level design space. They now found extensive applications photochemical Therefore, perspective serves guideline designing toward sustainable has significant implications future development broad area solar-to-chemical conversion research.

Language: Английский

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Rational Design of Conjugated Microporous Polymer Photocatalysts with Definite D−π–A Structures for Ultrahigh Photocatalytic Hydrogen Evolution Activity under Natural Sunlight

ACS Catalysis, Journal Year: 2022, Volume and Issue: 13(1), P. 204 - 212

Published: Dec. 13, 2022

Organic polymers with conjugated architectures have been widely exploited as photocatalyst materials for hydrogen generation. However, it is still an enormous challenge to develop photocatalysts high generation activity under natural sunlight, which pretty significant practical applications. Herein, two microporous polymer definite D−π–A structures are designed and prepared using dibenzo[g,p]chrysene or pyrene planar architecture electron donors, thiophene a π-spacer, dibenzo[b,d]thiophene-S,S-dioxide acceptor. Benefiting from the efficient separation of light-generated electrons/holes due structure broad light absorption range, bare Py-TP-BTDO could deliver photocatalytic evolution rate (HER) 115.03 mmol h–1 g–1 upon exposure visible (λ > 420 nm). Impressively, outdoor experiment reveals that abundant continuous bubbles be produced fast visually observed sunlight by film large active area 120 cm2. A water-drainage further demonstrates 1224 mL gas 25 mg 3 wt % Pt cocatalyst in 7 h, corresponding HER 312.24 g–1, represents state art organic date. The suggests potential developed applications production.

Language: Английский

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Donor-acceptor carbazole-based conjugated microporous polymers as photocatalysts for visible-light-driven H2 and O2 evolution from water splitting

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 316, P. 121624 - 121624

Published: June 16, 2022

Language: Английский

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An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

Small, Journal Year: 2022, Volume and Issue: 18(28)

Published: June 10, 2022

Conjugated microporous polymers (CMPs) with donor-acceptor (D-A) molecular structure show high photocatalytic activity for hydrogen evolution due to the efficient light-induced electron/hole separation, which is mostly determined by nature of electron donor and acceptor units. Therefore, selection holds key point construct performance polymer photocatalysts. Herein, two dibenzo[b,d]thiophene-S,S-dioxide (BTDO) containing CMP photocatalysts using tetraphenylethylene (TPE) or dibenzo[g,p]chrysene (DBC) as investigate influence geometry on are design synthesized. Compared twisted TPE donor, DBC has a planar extended π-conjugation, promotes charges transmission separation. As result, DBC-BTDO produced from shows remarkable rate (HER) 104.86 mmol h-1 g-1 under full arc light (λ > 300 nm), much higher than that TPE-BTDO (1.80 ), demonstrating can be an constructing D-A evolution.

Language: Английский

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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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Unveiling the exciton dissociation dynamics steered by built-in electric fields in conjugated microporous polymers for photoreduction of uranium (VI) from seawater

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 662, P. 377 - 390

Published: Feb. 9, 2024

Language: Английский

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Conjugated porous polymers for photocatalysis: The road from catalytic mechanism, molecular structure to advanced applications

EnergyChem, Journal Year: 2022, Volume and Issue: 4(6), P. 100094 - 100094

Published: Oct. 7, 2022

Language: Английский

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Toward high-performance dibenzo[g,p]chrysene-based conjugated polymer photocatalysts for photocatalytic hydrogen production through donor-acceptor-acceptor structure design

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 459, P. 141553 - 141553

Published: Jan. 24, 2023

Language: Английский

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