Institutional Repository of Key Laboratory of Marine Environmental Corrosion and Bio-fouling, IOCAS
|Place of Conferral||中国科学院海洋研究所|
|Keyword||海洋防污 光催化 纳米酶 杀菌机制 光致阴极保护|
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S2‒、Se2‒取代MnCo2O4中的O2‒，合成了新型负载结构Mn-Co-S-Se/NF（MnCo2SxSe4–x/NF）仿生纳米酶材料。随着S/Se摩尔比的不同，MnCo2SxSe4–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MnCo2S3.1Se0.9/NF活性最优。MnCo2S3.1Se0.9/NF具有比天然辣根过氧化物酶更高的Vmax（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‒，MnCo2S3.1Se0.9/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MnCo2S3.1Se0.9/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 (MnCo2SxSe4–x)/Ni foam (NF) are synthesized by introducing S2– and Se2– in MnCo2O4/NF with a facile hydrothermal approach. With the different molar ratios of S/Se, the surface of MnCo2SxSe4–x/NF shows different morphology and the catalytic activity also presents regular changes. MnCo2S3.1Se0.9/NF possesses a high enzyme-like ability with higher Vmax than natural horseradish peroxidase. Due to the outstanding peroxidase-like activity, MnCo2S3.1Se0.9/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 MnCo2S3.1Se0.9/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.
|Subject Area||环境科学技术 ; 环境工程学|
|MOST Discipline Catalogue||工学|
|Funding Project||Natured Science Foundation of China ; Natured Science Foundation of China|
|Table of Contents|
|连雨萌. 绿色催化材料的设计、负载及海洋防污应用研究[D]. 中国科学院海洋研究所. 中国科学院大学,2022.|
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