Photons, Excitons, and Electrons in Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32161 - 32205

Опубликована: Ноя. 18, 2024

Covalent organic frameworks (COFs) are created by the condensation of molecular building blocks and nodes to form two-dimensional (2D) or three-dimensional (3D) crystalline frameworks. The diversity with different properties functionalities large number possible framework topologies open a vast space well-defined porous architectures. Besides more classical applications materials such as absorption, separation, catalytic conversions, interest in optoelectronic COFs has recently increased considerably. electronic both their linkage chemistry can be controlled tune photon absorption emission, create excitons charge carriers, use these carriers photocatalysis, luminescence, chemical sensing, photovoltaics. In this Perspective, we will discuss relationship between structural features properties, starting connectivity, layer stacking 2D COFs, control over defects morphology including thin film synthesis, exploring theoretical modeling structural, electronic, dynamic discussing recent intriguing focus on photocatalysis photoelectrochemistry. We conclude some remarks about present challenges future prospects powerful architectural paradigm.

Язык: Английский

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Theoretical investigation of a C₂N monolayer as a bifunctional electrocatalyst for rechargeable non-aqueous Li–air batteries

Journal of Materials Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Our work provides a detailed mechanistic pathway for the oxygen reduction reaction during discharging process and potentiality of C 2 N monolayer as cathode catalyst in non-aqueous Li–air batteries.

Язык: Английский

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

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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

Язык: Английский

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Photocarrier Dynamics of Two-Dimensional Aza-Fused Covalent Organic Frameworks as Bifunctional Photocatalysts toward Overall Water Splitting

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(45), С. 62043 - 62051

Опубликована: Окт. 31, 2024

Designing high-efficiency bifunctional photocatalysts toward photoinduced overall water splitting is one of the most promising and challenging research directions for clean energy generation. By employing static electronic structure calculation nonadiabatic molecular dynamics (NAMD) simulation, we herein established a recently synthesized two-dimensional (2D) aza-fused covalent organic framework (aza-COF) as potential photocatalyst reactions. Our calculated results reveal that overpotentials hydrogen evolution reaction oxygen are only 0.06 0.31 V, respectively, at pH = 4. The photoexcited charge carriers studied through NAMD simulation predicts electron–hole recombination time (25.15 ns), this confirms photogenerated electron hole migrate to active sites occurrence before they recombine. Therefore, our suggest 2D aza-COFs exhibit great metal-free single-material under visible light.

Язык: Английский

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Controlling the Charge Carrier Dynamics of o-B₂N₂ Monolayer through Pnictogen Family Atoms Doping

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(37), С. 9388 - 9396

Опубликована: Сен. 6, 2024

In the quest for an efficient solar energy harvester, one should focus on materials that have a large carrier lifetime. Using time-domain density functional theory combined with nonadiabatic molecular dynamics simulations, we herein established single-atom doping from pnictogen family can effectively alter electron-hole recombination time in o-B

Язык: Английский

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Porous solids for energy applications

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(20)

Опубликована: Ноя. 26, 2024

Язык: Английский

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