纳米Co3O4 复合有机硅基低表面能涂层的制备与防污机制研究

doi:10.11902/1005.4537.2025.145

中国腐蚀与防护学报

2026, Vol. 46

Issue (2): 417-429 CSTR: 32134.14.1005.4537.2025.145 DOI: 10.11902/1005.4537.2025.145

研究报告

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纳米Co₃O₄ 复合有机硅基低表面能涂层的制备与防污机制研究

李子豪¹^,²^,³, 李梦楠²^,³^,⁴, 翟晓凡¹^,²^,³(

), 孙佳文²^,³(

), 叶素娟⁴

^1.齐鲁工业大学生物工程学院济南 250353
^2.中国科学院海洋研究所海洋关键材料全国重点实验室海洋环境腐蚀与生物污损实验室青岛 266071
^3.广西科学院广西海洋科学院广西海洋环境科学重点实验室南宁 530007
^4.青岛科技大学化学与分子工程学院教育部光电传感与生命科学分析化学重点实验室青岛 266042

Preparation and Antifouling Performance of Nano-Co₃O₄ Composite Silicone-based Low Surface Energy Coating

LI Zihao¹^,²^,³, LI Mengnan²^,³^,⁴, ZHAI Xiaofan¹^,²^,³(

), SUN Jiawen²^,³(

), YE Sujuan⁴

^1.School of Bioengineering, Qilu University of Technology, Jinan 250353, China
^2.Key Laboratory of Advanced Marine Materials, Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China
^3.Guangxi Key Laboratory of Marine Environmental Science, Guangxi Academy of Marine Sciences, Guangxi Academy of Sciences, Nanning 530007, China
^4.Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE; College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

引用本文:

李子豪, 李梦楠, 翟晓凡, 孙佳文, 叶素娟. 纳米Co₃O₄ 复合有机硅基低表面能涂层的制备与防污机制研究[J]. 中国腐蚀与防护学报, 2026, 46(2): 417-429.
Zihao LI, Mengnan LI, Xiaofan ZHAI, Jiawen SUN, Sujuan YE. Preparation and Antifouling Performance of Nano-Co₃O₄ Composite Silicone-based Low Surface Energy Coating[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(2): 417-429.

全文: PDF(14592 KB) HTML

摘要:

提出了一种基于纳米酶催化杀菌与有机硅低表面能协同作用的新型防污策略。将具有过氧化物酶活性的纳米Co₃O₄进行表面改性，然后引入到有机硅树脂中，成功制备了新型纳米复合涂层PDMS/PEG-F-Co₃O₄，该涂层表现出较好的基底附着力(GFE：(1.72 ± 0.05) MPa；钢：(1.87 ± 0.09) MPa)、疏水性(105.3 ± 1.2)°和低表面能特性(21.1 ± 2.5) mJ/m²。此外，由于纳米Co₃O₄的催化杀菌与有机硅低表面能防污的双重作用，涂层静态防污性能显著提升，对铜绿假单胞菌和金黄色葡萄球菌的抑菌率分别达到(93.1 ± 1.5)%和(92.2 ± 1.4)%，同时使小球藻附着量降低91.6%。为开发高效环保的防污涂层提供了新思路。

关键词 ：防污涂层, 低表面能, 有机硅, 纳米酶, Co₃O₄

Abstract：

Hereon, a novel strategy of synergistic nano enzyme-catalyzed sterilization and low surface energy antifouling was proposed. Initially, hollow tetrahedral nano-Co₃O₄ with peroxidase-like activity was synthesized, followed by surface modification using isophorone diisocyanate (IPDI) and castor oil. The successful modification was then confirmed through comprehensive material characterization. Concurrently, polyethylene glycol-based polyurethane (PEG-DAF) was combined with silicone-polyurea (PDMS-PU) to form a polymer resin matrix. The surface-modified nano-Co₃O₄ was then incorporated into this mixed resin, successfully fabricating a novel nanocomposite coating designated as PDMS/PEG-F-Co₃O₄. The resulting nanocomposite coating demonstrated outstanding comprehensive performance. The results demonstrated that the coating exhibits excellent substrate adhesion (GFE: (1.72 ± 0.05) MPa, steel: (1.87 ± 0.09) MPa), with water contact angle (105.3 ± 1.2)° and low surface energy (21.1 ± 2.5) mJ/m². More importantly, the synergistic interplay between the nano enzyme-catalyzed antibacterial activity of Co₃O₄ nanoparticles and the low surface energy characteristics of silicone significantly enhanced the static antifouling performance of the coating. The composite coating demonstrated exceptional antibacterial efficacy, achieving inhibition rates of (93.1 ± 1.5)% against Pseudomonas aeruginosa and (92.2 ± 1.4)% against Staphylococcus aureus, along with remarkable inhibition of Chlorella adhesion (91.6 ± 0.9)%. Furthermore, radical trapping experiments were systematically conducted to elucidate and validate the underlying antifouling mechanism. This work established a novel approach for developing high-performance and eco-friendly antifouling coatings.

Key words： antifouling coating low surface energy silicone nanozyme Co₃O₄

收稿日期: 2025-05-14 32134.14.1005.4537.2025.145

ZTFLH:

TG174

基金资助:国家自然科学基金(42376204);国家自然科学基金(42406206);广西科技计划项目(桂科AA23026007);山东省自然科学基金(ZR2022MD023);中国科学院国际伙伴计划(058GJHZ2023058FN)

通讯作者: 翟晓凡，E-mail：zhaixf@qdio.ac.cn，研究方向为海洋微生物腐蚀防治;
孙佳文，E-mail：sunjiawen@qdio.ac.cn，研究方向为海洋防污涂层

作者简介: 李子豪，男，2000年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.145 或 https://www.jcscp.org/CN/Y2026/V46/I2/417

图1 纳米Co3O4的制备与表面改性方法及聚合物PDMS-PU和PEG-DAF的合成路线

图2 Co3O4改性前后的FTIR和XRD谱图

图3 Co3O4和F-Co3O4的XPS扫描全谱以及Co、O、C和N元素的高分辨率光谱图

图4 Co3O4和F-Co3O4的SEM及TEM图像

图5 聚合物在CDCl3中的1H NMR光谱，GPC曲线及FTIR谱图

表1 聚合物PDMS-PU, PEG-DAF和PDMS/PEG的Mn、Mw和PDI

图6 涂层的水接触角和表面能

图7 涂层在GFE和钢片上的附着强度

图8 铜绿假单胞菌和金黄色葡萄球菌黏附在涂层上的荧光图像及相应的表面活死菌的覆盖率和抗黏附率

图9 小球藻附着在涂层上的荧光图像以及在涂层表面的定量沉降密度和抗黏附率

图10 PDMS/PEG和PDMS/PEG-F-Co3O4添加捕获剂后在H2O2条件下的荧光显微镜图像和相应的细菌覆盖率直方图及PDMS/PEG和PDMS/PEG-F-Co3O4的⋅O2-和⋅OH的EPR光谱

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