Push-pull-pull interactions of 2D imide-imine-based covalent organic framework to promote charge separation in photocatalytic hydrogen production

Photocatalytic hydrogen production through water splitting provides a promising route towards renewable energy generation. However, constructing photocatalytically active covalent organic frameworks with high charge separation remains challenging. Herein, we demonstrate for the first time the use of...

Full description

Saved in:
Bibliographic Details
Published in:Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2024-05, Vol.12 (18), p.179-1798
Main Authors: Mekhemer, Islam M. A, Elsenety, Mohamed M, Elewa, Ahmed M, Huynh, Khanh Do Gia, Samy, Maha Mohamed, Mohamed, Mohamed Gamal, Dorrah, Dalia M, Hoang, Dung Chau Kim, Musa, Ahmed Fouad, Kuo, Shiao-Wei, Chou, Ho-Hsiu
Format: Article
Language:English
Subjects:
Charge transfer
Covalence
Evolution
Hydrogen
Hydrogen evolution reactions
Hydrogen production
Irradiation
Light irradiation
Photocatalysis
Photoexcitation
Renewable energy
Separation
Thermal stability
Water splitting
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Photocatalytic hydrogen production through water splitting provides a promising route towards renewable energy generation. However, constructing photocatalytically active covalent organic frameworks with high charge separation remains challenging. Herein, we demonstrate for the first time the use of 2D imide-imine-based covalent organic frameworks as new photocatalysts for the hydrogen evolution reaction (HER) under visible light irradiation. The main achievement is incorporating donor and dual acceptors, including weak electron-deficient imine and strong electron-deficient imide groups within the 2D COF backbone that create favorable push-pull-pull intramolecular charge transfer to promote charge separation after photoexcitation. DFT and NBO calculations revealed the strong integration of donor and dual acceptors with a synergistic interplay enhancing spatial charge transfer and separation. The synthesized COFs show significantly high thermal stability >400 °C with a high energy barrier for degradation. Moreover, Py-DNII-COF exhibited a 104-fold enhancement in hydrogen evolution compared to TFPB-DNII-COF. Py-DNII-COF demonstrated excellent stability and hydrogen evolution of 625 μmol h −1 g −1 over 48 hours. This study demonstrated the synthesis of imide-imine based COFs, boosting the electrical conductivity in the network due to the presence of dual electron-acceptor centers. This makes them efficient for light-induced hydrogen evolution reactions.
ISSN:2050-7488
2050-7496
DOI:10.1039/d4ta01108b