Citation: Shanshan Cheng, Lingjing Yu, Siqi Liu, Hongyi Gao, Changan Wang, Zeyang Song, Supakorn Boonyuen, Muye Niu, Ge Wang. Regulating electron transfer between valence-variable Fe and Cu sites in bimetallic MOFs to enhance ROS generation for day-night antibacterial efficacy[J]. Chinese Chemical Letters, ;2026, 37(6): 111553. doi: 10.1016/j.cclet.2025.111553 shu

Regulating electron transfer between valence-variable Fe and Cu sites in bimetallic MOFs to enhance ROS generation for day-night antibacterial efficacy

Shanshan Cheng ^{a, 1} ,
Lingjing Yu ^{a, 1} ,
Siqi Liu ^a ,
Hongyi Gao ^{a, b, *,} ,
Changan Wang ^a ,
Zeyang Song ^a ,
Supakorn Boonyuen ^c ,
Muye Niu ^b ,
Ge Wang ^{a, *,}

a.
Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
b.
Shunde Graduate School, University of Science and Technology Beijing, Shunde 528399, China
c.
Department of Chemistry, Faculty of Science and Technology, Thammasat University, Pathumthani 12120, Thailand

hygao@ustb.edu.cn

gewang@ustb.edu.cn

Received Date: 5 April 2025
Revised Date: 4 July 2025
Accepted Date: 7 July 2025
Available Online: 8 July 2025

Figures(5)

Reactive oxygen species (ROS) mediated oxidative stress represents a pivotal mechanism in antimicrobial activity, but most ROS-releasing materials require external stimuli, restricting their efficacy for continuous day-night applications. In this study, we present a novel substitution strategy to synthesize Cu-doped bimetallic organic frameworks with coordinatively unsaturated metal sites (CUMS), aiming to enhance ROS-mediated antimicrobial efficacy by regulating electron transfer between Cu and valence-variable Fe sites through Cu doping. The incorporation of Cu sites effectively modifies the electronic structure of Fe sites and optimizes the energy band structure of Fe-MIL-101, facilitating the effective electron transfer between the metal sites. Furthermore, the thermal treatment promotes the formation of coordinatively unsaturated electron-rich Fe active sites, significantly enhancing the O₂ adsorption and activation, which in turn boosts ROS generation. Notably, the 0.5Cu-Fe-MIL-101(CUMS) exhibits remarkable ROS generation capability, demonstrates a 99.99% antibacterial effectiveness against Escherichia coli (E. coli) within 30 min of light exposure, and maintains a 99.99% antimicrobial efficacy after 4 h in darkness, thus achieving robust day-night antimicrobial activity. Density functional theory calculations and X-ray photoelectron spectroscopy (XPS) analyses confirm that the enhanced electron transfer between Cu and Fe sites facilitates the adsorption of O₂ and H₂O₂ on the valence-variable Fe sites, promoting the spontaneous generation of ·O₂⁻ and ·OH, which induce oxidative stress and membrane damage in bacterial cells. This study highlights the potential of strategically tailoring the electronic properties surrounding the coordinatively unsaturated metal sites in bimetallic metal organic frameworks (MOFs) for advanced antibacterial applications.
- Bimetallic MOFs,
- Electron transfer,
- Coordinatively unsaturated metal sites,
- Reactive oxygen species,
- Antibacterial activity
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