Schottky Junction and D–A₁–A₂ System Dual Regulation of Covalent Triazine Frameworks for Highly Efficient CO₂ Photoreduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(5)

Published: Nov. 2, 2023

Abstract Covalent triazine frameworks (CTFs) are emerging as a promising molecular platform for photocatalysis. Nevertheless, the construction of highly effective charge transfer pathways in CTFs oriented delivery photoexcited electrons to enhance photocatalytic performance remains challenging. Herein, engineering strategy is presented achieve efficient separation and transport both lateral vertical directions solar‐to‐formate conversion. Specifically, large π ‐delocalized ‐stacked Schottky junction (Ru‐Th‐CTF/RGO) that synergistically knits rebuilt extended network D–A 1 –A 2 system (multiple donor or acceptor units, Ru‐Th‐CTF) with reduced graphene oxide (RGO) developed. It verified single‐site Ru units Ru‐Th‐CTF/RGO act secondary electron acceptors direction multistage separation/transport. Simultaneously, covalently bonded regarded hole extraction layer, accelerating separation/transport photogenerated charges over full use reduction reaction. Thus, obtained photocatalyst has an excellent CO ‐to‐formate conversion rate (≈11050 µmol g −1 h ) selectivity (≈99%), producing state‐of‐the‐art catalyst heterogeneous formate without extra photosensitizer.

Language: Английский

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Selective Metal-Free CO₂ Photoreduction in Water Using Porous Nanostructures with Internal Molecular Free Volume

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23802 - 23813

Published: Oct. 23, 2023

The conversion of CO2 to a sole carbonaceous product using photocatalysis is sustainable solution for alleviating the increasing levels emissions and reducing our dependence on nonrenewable resources such as fossil fuels. However, developing photoactive, metal-free catalyst that highly selective efficient in reduction reaction (CO2RR) without need sacrificial agents, cocatalysts, photosensitizers challenging. Furthermore, due poor solubility water kinetically thermodynamically favored hydrogen evolution (HER), designing photocatalyst Here, we propose molecular engineering approach design photoactive polymer with high permeability low diffusivity, promoting mass transfer while suppressing HER. We have incorporated contorted triptycene scaffold "internal free volume (IMFV)" enhance gas active site by creating channels through inefficient packing chains. Additionally, introduced pyrene moiety promote visible-light harvesting capability charge separation. By leveraging these qualities, exhibited CO generation rate 77.8 μmol g-1 h-1, selectivity ∼98% good recyclability. importance IMFV was highlighted replacing unit planar scaffold, which led reversal favoring HER over CO2RR water. In situ electron paramagnetic resonance (EPR), time-resolved photoluminescence spectroscopy (TRPL), diffuse reflectance infrared Fourier transform (DRIFTS) techniques, further supported theoretical calculations, were employed enlighten mechanistic insight exclusively

Language: Английский

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Immobilization of metal active centers in reticular framework materials for photocatalytic energy conversion

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(22), P. 12907 - 12925

Published: Jan. 1, 2024

To enhance the economy and society's sustainability, prioritizing innovative, green energy conversion methods is essential.

Language: Английский

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Tuning redox activity in metal–organic frameworks: From structure to application

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 517, P. 216004 - 216004

Published: June 21, 2024

Language: Английский

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Recent advances in heteroatom-doped/hierarchically porous carbon materials: Synthesis, design and potential applications

Progress in Materials Science, Journal Year: 2024, Volume and Issue: unknown, P. 101408 - 101408

Published: Nov. 1, 2024

Language: Английский

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