海洋环境腐蚀与生物污损重点实验室知识库

随着对海洋资源的发掘，海洋生物污损对经济和社会的危害逐渐加重，开发稳定性高的多功能材料才能应对海洋生物污损。传统毒剂型防污涂层具有污染环境和毒害生物的危害，因此需要研发环境友好型防污材料。绿色催化防污材料是环境友好防污材料重要的组成部分，但是从应用角度看，目前材料综合防污性能还存在不足。为提高性能，并探求防污工程化应用的可行性，开展了本论文的研究工作。首先针对单纯的光催化剂在无光照环境中不具有催化防污作用的难题，提出光酶偶联催化防污体系的设计理念，通过多种催化防污性能的集成提高了环境适应性和催化防污活性；其次针对绿色催化防污材料以粉体形式存在的工程化应用难题，利用无机纳米晶体原位生长技术，借助拓扑转化实现了绿色催化活性防污材料在支撑骨架（如泡沫镍）上的稳定负载，大幅提高材料的稳定性和重复利用性，可满足水体环境实际应用需求；最后通过材料复合，制备了具有防污活性的光电极，并可应用于光致阴极保护，研究了材料的防腐防污性能和机制，进一步拓展了绿色催化防污材料在海洋腐蚀与生物污损领域的应用场景。具体研究内容为：

1、采用一步沉淀法制备了不同摩尔比的AgBr/Ag₂MoO₄纳米颗粒。用XPS、SEM等手段对AgBr/Ag₂MoO₄的形貌和组成进行了分析，不同摩尔比AgBr/Ag₂MoO₄所负载的AgBr的量不同，使得催化活性也有所不同。摩尔比为1:1的AgBr/Ag₂MoO₄具有良好的光催化活性，对罗丹明B的降解率为100%，对盐酸四环素的降解率接近80%。酶反应体系和光催化反应体系均可产生∙O₂^‒，单独光催化体系中可同时产生∙OH，借助这些活性自由基可成功杀灭大肠杆菌（E. coli）和金黄色葡萄球菌（S. aureus），达到广谱抗菌的目的。AgBr/Ag₂MoO₄在可见光和H₂O₂协同作用下，对E. coli和S. aureus的杀灭率在短时间内就可达到100%。AgBr/Ag₂MoO₄复合材料是一种具有双重催化活性的新型光酶偶联型杀菌防污剂，在环境污染和杀菌防污领域具有一定应用前景。

2、通过水热法在对负载在泡沫镍（NF）上的MnCo₂O₄纳米阵列进行可控硫化和硒化，即S^2‒、Se^2‒取代MnCo₂O₄中的O^2‒，合成了新型负载结构Mn-Co-S-Se/NF（MnCo₂S_xSe_4–x/NF）仿生纳米酶材料。随着S/Se摩尔比的不同，MnCo₂S_xSe_4–x/NF的表面形貌表现出不同的生长规律，催化活性也有所不同，其中以MnCo₂S_3.1Se_0.9/NF活性最优。MnCo₂S_3.1Se_0.9/NF具有比天然辣根过氧化物酶更高的V_max（最大反应速度），证明其模拟酶反应活性比天然酶更高。由于类过氧化物酶样活性能产生活性自由基∙O₂^‒，MnCo₂S_3.1Se_0.9/NF表现出对E. coli和S. aureus的广谱杀菌性能。在重复使用实验中，经过25次循环测试后，酶活性依旧保持稳定；经过10次循环杀菌测试后，杀菌性能略微降低，证明MnCo₂S_3.1Se_0.9/NF具有较高稳定性和重复使用性。

3、通过水热法制备MoS₂和MoSe₂两种半导体材料，设计构建一种新型的MoS₂&MoSe₂异质结薄膜光电极来探究其对304不锈钢的光致阴极保护性能以及防污性能。对不同摩尔比MoS₂&MoSe₂薄膜材料进行形貌、元素分析，其中MoS₂表面为褶皱状，可提供更多活性位点。在EIS测试中摩尔比为2:1的MoS₂&MoSe₂的电荷转移电阻R₁为20.76 Ω cm²，其瞬态光电流响应为134 μA/cm²，MoS₂&MoSe₂异质结薄膜具有较优的光生电子-空穴分离效率。分析其光致阴极保护性能，其光致电流密度变化和电位降最高达到80 μA/cm²和200 mV，并揭示了对304不锈钢的保护机理；MoS₂&MoSe₂薄膜材料也具备一定的防污性能，其防污过程起作用的自由基为h⁺和∙O₂^‒，为实际海洋环境应用打下基础。

As for the excavation of the marine resources, harm to the economy, society, and human health from marine biofouling increases gradually, the multi-functional materials of high stability should be developed. Traditional toxic antifouling coating has the harm of environmental pollution and toxic organisms, so it is necessary to develop environment-friendly antifouling materials. Green catalytic antifouling material is an important part of environment-friendly antifouling materials. However, from the perspective of application, the comprehensive antifouling performance of materials is still inadequate. In order to improve the performance and explore the feasibility of antifouling engineering application, the research work of this paper was carried out. Firstly, the design concept of coupled photo-enzyme catalytic antifouling system was proposed to solve the problem that simple photocatalyst has no catalytic antifouling effect in the dark. The environmental adaptability and catalytic antifouling activity were improved through the integration of various catalytic antifouling properties. Secondly, in order to solve the difficulty of application about green catalytic materials powder, inorganic nanocrystals were used in situ growth technology with the help of topological transformation, which achieved green catalytic activity antifouling materials. And the materials were supported on the frame of nickel foam, which improved the stability and reusability of the materials and could meet the demand of practical application of aquatic environment. Finally, the photoelectrode with antifouling activity was prepared through constructing composites, which could be applied to photocathodic protection. The performance and mechanism of antifouling and anticorrosion about the material were studied, which further expanded the application scene of green catalytic antifouling materials in the field of marine corrosion and biofouling. The following were the research contents:

1. AgBr/Ag₂MoO₄ nanoparticles with different molar ratios were prepared by a one-step precipitation method. The morphology and component of AgBr/Ag₂MoO₄ were analyzed by several characterizations including XPS, SEM, et al., which showed that the loaded content of AgBr was different in different molar ratios, making the catalytic activity different. 1:1AgBr/Ag₂MoO₄ displayed better enzyme-like activity than that of the pure AgBr and Ag₂MoO₄. It can depict that AgBr/Ag₂MoO₄ with a 1:1 molar ratio possessed excellent photocatalytic activity with a 100% degradation rate of rhodamine B, and nearly 80% degradation rate of tetracycline hydrochloride. ∙O₂^‒ can be produced from the enzyme reaction system and the photocatalytic system, and ∙OH can be generated under visible light, which can successfully kill Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The sterilization rate of AgBr/Ag₂MoO₄ with visible light and H₂O₂ achieved 100% in a short time toward E. coli and S. aureus. The AgBr/Ag₂MoO₄ composite, as the bactericidal catalyst, with dual catalytic activities is a promising material in the field of environmental pollution and bacterial infection.

2. Mn-Co-S-Se (MnCo₂S_xSe_4–x)/Ni foam (NF) are synthesized by introducing S^2– and Se^2– in MnCo₂O₄/NF with a facile hydrothermal approach. With the different molar ratios of S/Se, the surface of MnCo₂S_xSe_4–x/NF shows different morphology and the catalytic activity also presents regular changes. MnCo₂S_3.1Se_0.9/NF possesses a high enzyme-like ability with higher V_max than natural horseradish peroxidase. Due to the outstanding peroxidase-like activity, MnCo₂S_3.1Se_0.9/NF also exhibits broad-spectrum bactericidal performance towards Escherichia coli and Staphylococcus aureus which stems from the formation of ·O₂^– from H₂O₂. In the reutilization experiment, the enzyme-like activity keeps a stable value after 25 cyclic tests and the bactericidal performance is still stable after 10 cyclic tests, proving that MnCo₂S_3.1Se_0.9/NF possesses relative stability and reusability.

3. MoS₂ and MoSe₂ semiconductor materials were prepared by hydrothermal method, and a novel MoS₂&MoSe₂ heterojunction film photoelectric electrode was designed and constructed to explore its photocathodic protection and antifouling property for 304 stainless steel. The morphology and elemental analysis of MoS₂ & MoSe₂ thin film materials with different molar ratios were carried out. The MoS₂ surface was wrinkled, which could provide more active sites. In the EIS test, the charge transfer resistance of MoS₂&MoSe₂ with a 2:1 molar ratiois 20.76 Ωcm², and its transient photocurrent response is 134 μA/cm². The separation efficiency of photo-generated electrons and holes in MoS₂&MoSe₂ heterojunction film was high. The change of photoinduced current density and potential were up to 80 μA/cm² and 200 mV, which reveals the corresponding mechanism of photocathodic protection. MoS₂&MoSe₂ film material has certain antifouling properties, the main free radicals in the antifouling application are h⁺ and ∙O₂^‒, which lays a foundation for practical applications in marine environment.

第一章 绪论.... 1

1.1 海洋生物污损... 1

1.1.1 海洋生物污损概述... 1

1.1.2 海洋生物污损发生过程... 1

1.1.3 防护措施及研究进展... 2

1.2 绿色催化防污材料研究现状... 5

1.2.1 绿色催化防污方法作用机制... 5

1.2.2 光催化绿色防污研究... 8

1.2.3 Ag基催化材料... 10

1.2.4 TMDs催化材料... 12

1.2.5 其他绿色催化防污材料... 15

1.3 选题依据和研究内容... 15

第二章 AgBr/Ag2MoO4光酶协同材料的可控制备与防污机制研究.... 17

2.1 前言... 17

2.2 材料与方法... 18

2.2.1 材料与试剂... 18

2.2.2 仪器与设备... 19

2.2.3 材料制备... 20

2.2.4 材料表征... 21

2.2.5 模拟酶性能与机理研究... 21

2.2.6 光催化性能与机理研究... 22

2.2.7 光酶偶联协同防污性能与机制研究... 23

2.3 结果与讨论... 23

2.3.1 材料表征... 23

2.3.2 模拟酶活性... 29

2.3.3 模拟酶催化机理... 31

2.3.4 光催化活性... 33

2.3.5 光催化机理... 34

2.3.6 光酶协同防污杀菌应用... 37

2.3.7 稳定性测试... 38

2.4 本章小结... 40

第三章 负载化Mn-Co-S-Se纳米酶材料的可控制备与防污机制研究.... 42

3.1 前言... 42

3.2 材料与方法... 43

3.2.1 材料与试剂... 43

3.2.2 仪器与设备... 44

3.2.3 材料制备... 44

3.2.4 材料表征... 45

3.2.5 模拟酶性能及机理研究... 45

3.2.6 模拟酶杀菌防污性能研究... 45

3.2.7 重复利用性和稳定性研究... 46

3.3 实验结果与讨论... 46

3.3.1 材料表征... 46

3.3.2 模拟酶性能... 52

3.3.3 模拟酶催化机理... 55

3.3.4 模拟酶防污杀菌... 55

3.3.5 模拟酶循环应用... 59

3.4 本章小结... 61