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ZIF-8 modified by isocyanate as a photocatalytic antibacterial agent

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Abstract

Zeolite imidazole skeleton (ZIF-8) is a promising option for self-cleaning of building exterior walls due to its large specific surface area, high antibacterial activity and low biotoxicity. However, it suffers from low antibacterial efficiency and yield under visible light irradiation. To address the issues, we developed the photocatalytic materials T-ZIF-8-TDI (thermally treated-ZIF-8-toluene 2,4-diisocyanate) by modifying ZIF-8 with thermal oxygen sensitization and chemical bonding. The results show that the yield of T-ZIF-8-TDI photocatalytic antibacterial agent is increased to 11.5 times of that of T-ZIF-8, while maintaining the crystal structure of T-ZIF-8 and thermal stability up to 60 °C. Furthermore, T-ZIF-8-TDI exhibits extended optical response range to the near-infrared region, significantly narrowed band gap, improved photogenerated electron–hole separation efficiency, reduced recombination rate, and excellent photocatalytic performance. When the concentration of antibacterial agent is 600 mg·L−1, the antibacterial rate of Escherichia coli (E. coli) reaches 99.99% irradiated by visible light for 30 min, and when the concentration of antibacterial agent is 200 mg·L−1, the antibacterial rate of Staphylococcus aureus (S. aureus) reaches 99.99% irradiated by visible light for 25 min. We also analyzed the reasons in detail from the aspects of bacterial species and antibacterial mechanism, and proposed the antibacterial mechanism of ·O2− and h+ as the main active species. These findings suggest that T-ZIF-8-TDI photocatalytic antibacterial agent has potential for use in self-cleaning of building exterior walls.

Graphical abstract

摘要

沸石咪唑骨架 (ZIF-8)具有比表面积大、抗菌活性高、生物毒性低等特性, 是一种极具前景的建筑外墙自洁净材料。但在可见光照射下, 其抗菌效率和产率较低。为解决这一问题, 本论文采用热氧敏化和化学键合法对ZIF-8进行改性, 研制出光催化材料T-ZIF-8-TDI。结果表明, T-ZIF-8-TDI光催化抗菌剂的产率比T-ZIF-8提高了11.5倍, 同时保持了T-ZIF-8的晶体结构, 60 °C 前其热性能保持稳定; T-ZIF-8-TDI的光响应范围扩展到近红外光区, 带隙明显缩小, 光生电子空穴分离效率大幅提高, 复合速率显著降低; 抗菌剂浓度为600 mg·L−1时, 可见光照射30 min, 对大肠杆菌的抗菌率达99.99%, 抗菌剂浓度为200 mg·L−1时, 可见光照射30 min, 对金黄色葡萄球菌的抗菌率达99.99%。我们从细菌种类和抗菌机理等方面详细分析了原因, 提出·O2−和h+为主要活性物种的抗菌机制。上述结果表明, T-ZIF-8-TDI光催化抗菌剂在建筑外墙自清洁方面具有潜在应用.

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Acknowledgements

This research was financially supported by the Projects of the Research and Development Project of New Materials and Chemical Engineering Research Institute of Shanxi Zhejiang University (No. 2021SX-AT010), the National Natural Science Foundation of China (No. 21972103), Innovation and entrepreneurship training program for college students (No. 202110112012).

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Authors and Affiliations

  1. College of Architecture, Taiyuan University of Technology, Taiyuan, 030024, China

    Yi-Ning Zhang & Chong-En Wang

  2. Key Laboratory of Interface Science and Engineering in Advanced Materials of Taiyuan University of Technology, Ministry of Education, Taiyuan, 030024, China

    Yi-Ning Zhang, Zhen Pei, Zi-Hao Wang & Li-Qiao Wei

  3. Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan, 030000, China

    Li-Qiao Wei

  4. Department of Materials Science and Engineering, Shanxi Institute of Technology, Yangquan, 045000, China

    Fen-Fen Liang

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  1. Yi-Ning Zhang
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Zhang, YN., Pei, Z., Wang, ZH. et al. ZIF-8 modified by isocyanate as a photocatalytic antibacterial agent. Rare Met. 43, 2708–2718 (2024). https://doi.org/10.1007/s12598-023-02507-6

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