Ultrafast Charge Dynamics in Nitrogen‐Rich Covalent Organic Frameworks for Hydrogen Peroxide Photosynthesis

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

Published: April 7, 2025

Abstract Four new tetrazine‐based COFs, DT‐COF‐ n ( = 0–3, indicating the number of ─OH groups), incorporating diamino‐bis‐tetrazine and hydroxy‐functionalized benzo‐tri‐carbaldehyde monomers are used to explore link between bonding reversibility in supramolecular chemistry photocatalytic H 2 O production. DT‐COFs exhibit an exceptionally high nitrogen content, with 72 atoms per pore structure, accounting for 50.3% framework composition‐far exceeding previously reported COFs less than 32% nitrogen. This density, coupled strong electron‐accepting nature tetrazine units azo linker, promotes charge separation stabilization, critical efficient photocatalysis. DT‐COF‐1, which includes a single hydroxyl group, shows highly ordered structure extended conjugation. led yield 4300 µmol g −1 h apparent quantum 14.1% at 420 nm under visible light water. With respect peroxide yield, DT‐COF‐1 outperforms most other produce peroxide. also achieves ultrafast intramolecular electron transfer (<500 fs) prolonged excited state lifetime (≈90 ps). In situ paramagnetic resonance spectroscopy DFT calculations suggest Yeager‐type absorption •− intermediate, favoring

Language: Английский

End-capping fluorination of vinylene-linked covalent organic frameworks for photocatalytic hydrogen peroxide production

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

Published: Jan. 1, 2025

Inspired by the concept of an “antenna”, a simple end-capping fluorination strategy enhances charge transport and oxygen adsorption, thereby boosting photocatalytic H 2 O production.

Language: Английский