Co3O4-Zn复合镀层制备及其模拟酶催化防污活性研究

doi:10.11902/1005.4537.2023.371

中国腐蚀与防护学报

2024, Vol. 44

Issue (5): 1164-1176 CSTR: 32134.14.1005.4537.2023.371 DOI: 10.11902/1005.4537.2023.371

研究报告

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Co₃O₄-Zn复合镀层制备及其模拟酶催化防污活性研究

蒋泽¹^,²^,³, 翟晓凡²^,³(

), 张雨²^,³, 孙佳文²^,³, 蒋全通²^,³, 王优强¹(

), 段继周²^,³(

), 侯保荣²^,³

1 青岛理工大学机械与汽车工程学院青岛 266520
2 中国科学院海洋研究所海洋环境腐蚀与生物污损重点实验室青岛 266071
3 海洋科学与技术试点国家实验室(青岛)海洋腐蚀与防护开放工作室青岛 266235

Preparation of Co₃O₄-Zn Composite Coating and Its Simulated Antifouling Activity of Enzymes Catalyst

JIANG Ze¹^,²^,³, ZHAI Xiaofan²^,³(

), ZHANG Yu²^,³, SUN Jiawen²^,³, JIANG Quantong²^,³, WANG Youqiang¹(

), DUAN Jizhou²^,³(

), HOU Baorong²^,³

1 School of Mechanical and Automotive Engineering, Qingdao University of Technology, Qingdao 266520, China
2 CAS Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China
3 Open Studio for Marine Corrosion and Protection, Pilot National Laboratory for Marine Science and Technology (Qingdao), Qingdao 266235, China

引用本文:

蒋泽, 翟晓凡, 张雨, 孙佳文, 蒋全通, 王优强, 段继周, 侯保荣. Co₃O₄-Zn复合镀层制备及其模拟酶催化防污活性研究[J]. 中国腐蚀与防护学报, 2024, 44(5): 1164-1176.
Ze JIANG, Xiaofan ZHAI, Yu ZHANG, Jiawen SUN, Quantong JIANG, Youqiang WANG, Jizhou DUAN, Baorong HOU. Preparation of Co₃O₄-Zn Composite Coating and Its Simulated Antifouling Activity of Enzymes Catalyst[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(5): 1164-1176.

全文: PDF(12151 KB) HTML

摘要:

将具有过氧化物酶催化活性的Co₃O₄纳米颗粒通过电沉积的方法与锌基体共沉积获得了新型的Co₃O₄-Zn金属镀层，在Co₃O₄和锌基体的共沉积过程中引入了超声波和油酸钠，在此过程中，超声波和油酸钠有力地促进了Co₃O₄在共沉积表面的分散和吸附。通过SEM、XRD、电化学测试等表征手段证明Co₃O₄以有效的结构复合到Zn基体中，而油酸钠的加入则有效地增加了Co₃O₄-Zn镀层中Co₃O₄的负载量。此外，还用大肠杆菌、金黄色葡萄球菌和铜绿假单胞菌3种典型污损细菌评估了Co₃O₄-Zn镀层的抗菌性能。Co₃O₄-Zn镀层对这3种细菌的抑制率超过98%，显示出高度和广谱的抗菌性能。研究还证明，Co₃O₄-Zn镀层在具有H₂O₂情况下会产生超氧自由基和羟基自由基，它们在抗菌过程中起着主导的作用。最后还对复合镀层的抗菌稳定性和耐腐蚀特性进行了验证，表明复合镀层表现出良好的抗菌稳定和耐腐蚀特点。该研究结果为模拟酶催化杀菌金属基镀层的发展提供了新的可能，也为涉海设备的防污措施提供了一种新的思路。

关键词 ： Co₃O₄-Zn镀层, 超声辅助, 模拟酶催化抗菌, 电沉积, 油酸钠

Abstract：

Nanoparticles Co₃O₄ with peroxidase catalytic activity were co-deposited with Zn by electrodeposition to obtain a novel Co₃O₄-Zn composite coating on Q235 carbon steel. Ultrasound and sodium oleate (NaoI) were introduced during the co-deposition of Co₃O₄ and Zn, which strongly promoted dispersion and adsorption of Co₃O₄ on the co-deposited surface coating. The characterization by SEM and XRD revealed that Co₃O₄ was obviously dispersed into the Zn matrix. The addition of NaoI effectively increased the deposited amount of Co₃O₄ in the Co₃O₄-Zn coatings. Besides, the antimicrobial performance of the Co₃O₄-Zn coatings was evaluated with three typical fouling bacteria, namely, Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), and Pseudomonas aeruginosa (P. aeruginosa). Results showed that the coverage of these three bacteria on Co₃O₄-Zn coatings decreased over 98%, illustrating that the Co₃O₄-Zn coatings showed high and broad-spectrum antimicrobial performance. It was also found that the Co₃O₄-Zn coating in the presence of hydrogen peroxide (H₂O₂) produced superoxide radicals (·O $2 -$ ) and hydroxyl radicals (·OH), which played dominant roles in the antimicrobial process. Finally, the antimicrobial stability and corrosion resistance of the composite coatings were also verified, and it was found that the composite coatings exhibited good antimicrobial stability and corrosion resistance characteristics. The results of this study provide a new possibility for the development of bactericidal coatings of simulated enzyme catalyst and a new solution for green antifouling.

Key words： Co₃O₄-Zn coating ultrasound assistance simulated enzyme-catalyzed antimicrobial electrodeposition sodium oleate

收稿日期: 2023-11-21 32134.14.1005.4537.2023.371

ZTFLH:

TG174

基金资助:国家自然科学基金(42376204);山东省自然科学基金(ZR2022MD023);青岛海洋科学与技术试点国家实验室山东省专项经费“问海计划”项目(2021WHZZB2303);中国科协青年人才托举计划(YESS20210201)

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与防治段继周，E-mail: duanjz@qdio.ac.cn，研究方向为海洋微生物腐蚀与生物污损的基础和应用研究王优强，E-mail: wyq1970301@126.com，研究方向为摩擦学与表面工程

Corresponding author: ZHAI Xiaofan, E-mail: zhaixf@qdio.ac.cnDUAN Jizhou, E-mail: duanjz@qdio.ac.cn

作者简介: 蒋泽，男，1994年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2023.371 或 https://www.jcscp.org/CN/Y2024/V44/I5/1164

表1 镀层的电沉积参数

图1 ZB，ZY，ZC和ZCY镀层的微观形貌

图2 Co3O4粉体和ZCY的SEM像及相应的EDS结果

图3 ZCY横截面的SEM像，及图中区域1的SEM像和EDS结果和区域2的SEM像和EDS线扫描结果

表2 EDS测试的复合镀层中Co和Zn含量

图4 镀层中Co3O4和Zn对应的XRD谱

图5 ZB、ZY、ZC和ZCY镀层电沉积过程中的电化学分析及用于拟合EIS数据的等效电路

图6 在加入和不加入过氧化氢的大肠杆菌溶液中浸泡2 h后ZB、ZY、ZC和ZCY镀层的荧光显微镜图像，及镀层上细菌覆盖率的相应直方图

图7 在加入H2O2的大肠杆菌、金黄色葡萄球菌和铜绿假单胞菌溶液中浸泡2 h后ZB和ZCY镀层的荧光显微镜图像和细菌覆盖率的相应直方图

图8 ZB和ZCY复合镀层在大肠杆菌溶液中持续8个循环期间的荧光显微镜图像及细菌覆盖率变化

图9 ZB和ZCY镀层在海水中的电化学测试结果以及EIS拟合等效电路图

表3 根据图9c的Tafel曲线计算出的自腐蚀电位和自腐蚀电流密度

图10 ZB和ZCY镀层在添加清除剂后在不加入和加入过氧化氢条件下的荧光显微镜图像，细菌覆盖率的相应直方图，以及ZCY的⋅O2-、h+和⋅OH的EPR光谱

图11 Co3O4-Zn复合镀层杀菌机理示意图

图12 Co3O4粉末在添加清除剂后在不加入和加入H2O2菌液中的杀菌情况

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