Insights into excitonic behavior in single-atom covalent organic frameworks for efficient photo-Fenton-like pollutant degradation

Chao Zhu; Mingzheng Yang; Bo Jiang; Lun Lu; Qile Fang; Yong Zheng; Shuang Song; Baoliang Chen; Yi Shen

doi:10.1038/s41467-025-56103-6

Insights into excitonic behavior in single-atom covalent organic frameworks for efficient photo-Fenton-like pollutant degradation

Nat Commun. 2025 Jan 17;16(1):790. doi: 10.1038/s41467-025-56103-6.

Authors

Chao Zhu¹, Mingzheng Yang¹, Bo Jiang¹, Lun Lu², Qile Fang³, Yong Zheng⁴, Shuang Song¹, Baoliang Chen⁵, Yi Shen^{6

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Affiliations

¹ Department of Environment, Zhejiang University of Technology, Hangzhou, 310014, China.
² State Environmental Protection Key Laboratory of Environmental Pollution Health Risk Assessment Ministry of Ecology and Environment, South China Institute of Environmental Sciences, Guangzhou, 510655, China.
³ Advanced Institute of Natural Sciences, Beijing Normal University at Zhuhai, Zhuhai, 519087, China.
⁴ College of Materials and Chemical Engineering, China Three Gorges University, Yichang, 443002, China.
⁵ Faculty of Agriculture, Life, and Environmental Sciences and Department of Environmental Science, Zhejiang University, Hangzhou, 310058, China.
⁶ Department of Environment, Zhejiang University of Technology, Hangzhou, 310014, China. [email protected].
⁷ Shaoxing Research Institute, Zhejing University of Technology, Shaoxing, 312000, China. [email protected].

PMID: 39824825
DOI: 10.1038/s41467-025-56103-6

Abstract

The generation of radicals through photo-Fenton-like reactions demonstrates significant potential for remediating emerging organic contaminants (EOCs) in complex aqueous environments. However, the excitonic effect, induced by Coulomb interactions between photoexcited electrons and holes, reduces carrier utilization efficiency in these systems. In this study, we develop Cu single-atom-loaded covalent organic frameworks (Cu_SA/COFs) as models to modulate excitonic effects. Temperature-dependent photoluminescence and ultrafast transient absorption spectra reveal that incorporating acenaphthene units into the linker (Cu_SA/Ace-COF) significantly reduces exciton binding energy (E_b). This modification not only enhances peroxymonosulfate adsorption at Cu active sites but also facilitates rapid electron transfer and promotes selective hydroxyl radical generation. Compared to Cu_SA/Obq-COF (E_b = 25.6 meV), Cu_SA/Ace-COF (E_b = 12.2 meV) shows a 39.5-fold increase in the pseudo-first-order rate constant for sulfamethoxazole degradation (0.434 min^-1). This work provides insights into modulating excitonic behavior in single-atom catalysts via linker engineering for EOCs degradation.

Abstract

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