Decoupling Interlayer Interactions Boosts Charge Separation in Covalent Organic Frameworks for High‐Efficiency Photocatalytic CO2 Reduction DOI

Liyang Qin,

Dazhong Sun, D.L. Ma

et al.

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Abstract Covalent organic frameworks (COFs) have emerged as promising photocatalysts owing to their structural diversity, tunable bandgaps, and exceptional light‐harvesting capabilities. While previous studies primarily focus on developing narrow‐bandgap COFs for broad‐spectrum solar energy utilization, the critical role of interlayer coupling in regulating charge transfer dynamics remains unclear. Conventional monolayer‐based theoretical models inadequately address effects that potentially hindering intralayer electron transport catalytic active sites. This work employs density functional theory (DFT) calculations investigate influence interactions imine‐based COFs. Theoretical analyses reveal bilayer architectures exhibit pronounced interference intramolecular processes which has not been observed monolayer models. Based these mechanistic insights, this designs two isomeric pyrene‐based incorporating identical donor (pyrene) acceptor (nickel bipyridine) units but with distinct strengths. Strikingly, optimized COF weakened demonstrates photocatalytic CO 2 reduction performance, achieving a evolution rate 553.3 µmol g −1 h 94% selectivity under visible light irradiation without additional photosensitizers or co‐catalysts. These findings establish engineering crucial design principle high‐performance COF‐based conversion applications.

Language: Английский

Decoupling Interlayer Interactions Boosts Charge Separation in Covalent Organic Frameworks for High‐Efficiency Photocatalytic CO2 Reduction DOI

Liyang Qin,

Dazhong Sun, D.L. Ma

et al.

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Abstract Covalent organic frameworks (COFs) have emerged as promising photocatalysts owing to their structural diversity, tunable bandgaps, and exceptional light‐harvesting capabilities. While previous studies primarily focus on developing narrow‐bandgap COFs for broad‐spectrum solar energy utilization, the critical role of interlayer coupling in regulating charge transfer dynamics remains unclear. Conventional monolayer‐based theoretical models inadequately address effects that potentially hindering intralayer electron transport catalytic active sites. This work employs density functional theory (DFT) calculations investigate influence interactions imine‐based COFs. Theoretical analyses reveal bilayer architectures exhibit pronounced interference intramolecular processes which has not been observed monolayer models. Based these mechanistic insights, this designs two isomeric pyrene‐based incorporating identical donor (pyrene) acceptor (nickel bipyridine) units but with distinct strengths. Strikingly, optimized COF weakened demonstrates photocatalytic CO 2 reduction performance, achieving a evolution rate 553.3 µmol g −1 h 94% selectivity under visible light irradiation without additional photosensitizers or co‐catalysts. These findings establish engineering crucial design principle high‐performance COF‐based conversion applications.

Language: Английский

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