Keto-enol tautomerism as dynamic electron/hole traps promote charge carrier separation for hydrogen peroxide photosynthesis

Abstract Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumul...

Full description

Saved in:
Bibliographic Details
Main Authors: Fang Ma, Tao Gao, Xiaodong Sun, Chunqiu Han, Yongye Wang, Anqiang Jiang, Ying Zhou, Guijie Liang, Huiqing Wang, Li Wang, Binbin Jia, Yingping Huang, Hongwei Huang, Xin Ying Kong, Hui Li, Niu Huang, Tianyi Ma, Liqun Ye
Format: Article
Language:English
Published: Nature Portfolio 2025-08-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-62286-9
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Abstract Covalent organic frameworks (COFs) are promising photocatalysts for H2O2 photosynthesis, but charge carrier separation remains a critical challenge. Donor-acceptor COFs enhance charge separation, but the slow kinetics of water oxidation and oxygen reduction reactions lead to carrier accumulation, thereby decreasing efficiency. Here, we report T-C type COFs (T = trap units, C = catalytic units), demonstrating that units with keto-enol tautomerism can serve as dynamic electron/hole traps (T) to mitigate Coulomb forces. This design effectively facilitates swift charge transfer and extends carrier lifetimes, thereby enhancing reactions at the C units. Imine COFs derived from 2,4,6-trihydroxybenzaldehyde (Tp) outperform those based on 1,3,5-benzenetricarboxaldehyde due to tautomerization. The optimal Tp COF (TpBpy) achieves an H2O2 generation rate of 37.9 μmol h⁻¹ (or 8350 μmol h⁻¹ g⁻¹) under simulated light, and a solar-to-chemical conversion efficiency of 0.038% in a flow reactor under natural sunlight. This work provides molecular design strategies and standard criteria for efficient H2O2 photocatalysts.
ISSN:2041-1723