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金属有机骨架材料在海洋腐蚀检测与防护中的应用研究
陈怀银
Subtype博士
Thesis Advisor李伟华
2019-05-17
Degree Grantor中国科学院大学
Place of Conferral中国科学院海洋研究所
Degree Discipline海洋腐蚀与防护
Keyword金属有机骨架 腐蚀检测和防护 亚硝酸盐 超疏水 自清洁
Abstract

腐蚀问题是整个世界都在面临和亟待解决的重大问题,其中海洋腐蚀问题更为严峻,给全世界带来巨大的经济损失和安全威胁。因此,大力发展应用于海洋腐蚀检测和防护新材料或新技术,对保障海洋工程装备或海洋构筑物的安全使用,降低国家和世界的经济损失以及保护世界人民的生命安全等具有重大意义。作为一类新型的多功能材料,金属有机骨架(Metal-organic frameworksMOFs)近些年来在气体存储、吸附分离、催化、传感、药物传输等各个领域都展示出了十分出色的应用前景。MOFs材料具有比表面积大、孔隙高度有序、尺寸和形貌可控、结构与功能可调等优点,在海洋腐蚀领域也有望发挥重要作用。然而,目前MOFs材料在该领域的研究报道还寥寥无几,因此开发MOFs材料在海洋腐蚀检测与防护的应用研究具有一定的可行性和创新意义。本文基于MOFs材料开展了腐蚀检测和防护的应用研究,包括MOF基电化学传感器对传统缓蚀剂——亚硝酸盐的传感检测以及MOFs基超疏水涂层或表面对碳钢和铜的腐蚀防护两部分内容。采用高灵敏检测缓蚀剂的方法进行腐蚀检测,在研究缓蚀剂作用机制和有效寿命的分析以及对环境有害的缓蚀剂监检测方面具有重要意义;采用构建MOFs基超疏水表面的方法研究材料结构、组成、形貌等因素对超疏水表面防腐性、稳定性、耐久性、自清洁等性能影响,总结防腐性能提升的规律和关键因素,为海洋腐蚀防护理论和应用研究提供新的方法和技术。本论文具体研究如下:

1)基于金纳米粒子(AuNPs)修饰的CuMOFCu-MOF),构建了用于传统缓蚀剂亚硝酸盐灵敏检测的电化学传感平台。在室温下,采用简单的湿法合成法制备了Cu-MOF,然后采用恒电位法在Cu-MOF修饰的玻璃碳电极(Cu-MOF/GCE)上电沉积AuNPs制备复合材料Cu-MOF/AuCu-MOF具有大比表面积和孔隙率,可提高亚硝酸盐的吸附,并且可防止AuNPs的聚集,使高导电性的AuNPs催化活性得以提高,因此Cu-MOF/Au对亚硝酸盐的氧化表现出协同催化作用。基于Cu-MOF/Au/GCE构建了亚硝酸盐传感平台,采用电流-时间测量技术进行定量检测。所制备的电化学传感平台对亚硝酸根的检测具有较高的灵敏度、选择性和稳定性,该法在0.1 ~ 40004000 ~ 10000 μmol L-1浓度范围内具有良好的线性关系,检测下限为82 nmol L-1。此外,该传感平台还可以用于实际样品中的亚硝酸盐检测。该研究拓宽了MOFs材料在构建新型电化学传感平台中的应用,为海洋腐蚀检测提供一个好的思路。

2)基于稳定的MOF材料——沸石咪唑酯骨架-8Zeolitic Imidazolate Framework-8ZIF-8)制备了超疏水防腐涂层,研究其在超疏水、自清洁、腐蚀防护、抗结冰、增强力和减小阻力等方面的性能。采用ZIF-8纳米粒子构建一定的粗糙度,以低表面能的全氟辛基三乙氧基硅烷(perfluorooctyltriethoxysilanePOTS)进行修饰制得超疏水涂料,并以环氧树脂作为粘结剂,增强超疏水涂层的稳定性、耐磨性和持久性。制备的超疏水涂层接触角可达168.2°具有良好的稳定性和耐久性,在空气中放置300天或者在3.5 wt.% NaCl溶液中浸泡60天后依然能保持超疏水性能。此外,还展示出优异防腐、自清洁、抗结冰、增强浮力和减小阻力等性能,其中在3.5 wt.% NaCl溶液中浸泡1 h后在低频率(0.01 Hz)下的阻抗模值与Q235碳钢相比提高了至少7个数量级。本论文提出的MOF基超疏水涂层的制备方法,不仅可以为简便制备高稳定性和耐久性的超疏水表面提供了很好的思路,而且还拓展了MOF材料在海洋腐蚀防护领域的应用。

3采用原位合成法在铜表面制备Cu-BTC/Cu2O膜,用低表面能的POTS进行疏水改性得到CuMOF超疏水膜,考察其在模拟海水中腐蚀防护性能。本实验的优点之一是Cu-BTC MOF膜合成具有绿色环保性直接采用Cu基体代替Cu盐参与反应,降低对环境污染的威胁先将基体在空气氛围下进行热处理使表面氧化,制得CuO/Cu2O双层膜,再在含均苯三甲酸(H3BTC)的反应溶液中进行水热反应CuOH3BTC反应即可得到Cu-BTC膜。分别采用扫描电子显微镜(SEM)、X射线衍射(XRD)、X光电子能谱(XPS)以及傅里叶红外变换光谱(FTIR)等手段对制备的样品表面进行表征分析,证明了Cu-BTC MOF膜的成功制备。通过接触角测试对比了铜基体经过处理后的表面浸润性变化,并对实验条件进行优化,最佳的超疏水表面接触角高达165.2°此外,还对制备的超疏水表面进行了自清洁和防腐性能测试,结果表明,本实验原位制备的MOF基超疏水膜除了具备令人满意的自清洁性能外,还对铜的腐蚀具有良好的防护性能,可为开发更多绿色环保的超疏水防腐表面提供思路和借鉴。

该研究使MOFs的应用研究范围在海洋科学领域得到了很好的拓展,为制备用于腐蚀检测的高灵敏电化学传感平台提供了新的思路,扩展了用于构建超疏水表面与涂层的新材料与新技术,证明了稳定的超疏水涂层在海洋腐蚀防护领域潜在的巨大应用前景,对深化MOFs更广领域的应用研究具有重要价值。

 

Other Abstract

Corrosion has been a major problem that occurred in the whole world and needs to be solved urgently. Especially, the problem of marine corrosion is more serious, which brings enormous economic losses and security threats to the whole world. Therefore, the vigorous development of new materials or technologies for marine corrosion detection and protection is of great significance for the purpose of ensuring the safe use of marine engineering equipment or marine structures, reducing the economic losses of the country and the world, and protecting the lives and safety of the people of the world. Metal-organic frameworks (MOFs), as a new class of multifunctional materials, have shown excellent application prospects in various fields such as gas storage, adsorption and separation, catalysis, sensing, drug delivery and so on in recent years. MOFs materials have many advantages, such as large specific surface area, highly ordered pores, controllable size and shape, adjustable structure and function, therefore, it is feasible and innovative to develop its application in marine corrosion detection and protection. In this dissertation, MOF materials have been prepared for the application research of corrosion detection and protection, including the sensing detection of the traditional corrosion inhibitor, nitrite, based on MOF-based electrochemical sensor and the fabrications of MOF-based superhydrophobic coatings for the corrosion protection against carbon steel and copper. It is of great significance to study the action mechanism of corrosion inhibitors and the analysis of their effective life as well as the monitoring and detection of corrosion inhibitors that are harmful to the environment. By fabricating MOFs-based superhydrophobic coatings or surfaces, study the influences of material structure, composition, topography and other factors on the properties of superhydrophobic surface, such as anticorrosion, stability, durability, self-cleaning, anti-icing and others, and summarizes the law of the anticorrosion performance and key factors, and provides new methods and techniques for marine corrosion protection theory and application research. The main research contents and results are as follows:

(1) An electrochemical sensing platform based on Cu-based metal-organic framework (Cu-MOF) decorated with gold nanoparticles (AuNPs) is constructed for the sensitive detection of the traditional corrosion inhibitor nitrite. Cu-MOF was synthesized by a simple wet chemical synthesis at room temperature. AuNPs were electrodeposited on Cu-MOF modified glass carbon electrode (Cu-MOF/GCE) using potentiostatic method. The AuNPs decorated Cu-MOF (Cu-MOF/Au) displays synergetic catalytic effect for the oxidation of nitrite due to the large surface area and porosity of Cu-MOF, which could prevent the aggregation of AuNPs and increase the adsorption of nitrite, combining with the high conductivity and excellent catalytic activity of AuNPs. A nitrite sensing platform was constructed based on Cu-MOF/Au/GCE, and amperometric technique was adopted for quantitative determination of nitrite. The prepared electrochemical sensing platform demonstrates high sensitivity, selectivity and good stability for the detection of nitrite. It shows two wide linear ranges of 0.1 – 4000 and 4000 – 10000 μmol L-1, and the low detection limit of 82 nmol L-1. Moreover, the sensing platform can also be used for the nitrite detection in real samples. This work would broaden the application of MOFs material in constructing more novel electrochemical sensing platforms.

(2) A very facile method that combining nano-sized zeolitic imidazolate framework-8 (ZIF-8) particles with low surface energy perfluorooctyltriethoxysilane (POTS) was used to fabricate superhydrophobic paint, which can be facilely and discretionarily coated on various substrate surfaces by spraying to form superhydrophobic coating. Furthermore, epoxy resin (EP) coating was used as adhesion agent to improve the mechanical robustness and durability of the superhydrophobic coating. The as-prepared ZIF-8/POTS/EP superhydrophobic coating shows not only excellent water-repellency (water contact angle = 168.2 °), self-cleaning, abrasion resistance, anti-icing, loading-increasing and drag-reducing, but also fantastic corrosion resistance and stability: the impedance modulus value of the ZIF-8/POTS/EP superhydrophobic coating at low frequency (0.01 Hz) was improved by 7 orders of magnitude than Q235 steel; and it maintained its superhydrophobic property after weathering in air for 300 days or immersing in 3.5 wt.% NaCl aqueous solution for 60 days. We believe that the facile method we proposed for fabrication of MOF-based superhydrophobic coating can not only promote the effortless and large-scale preparation of superhydrophobic surface and their practical applications in future, but also provide a novel way for applying MOF materials into more fields.

(3) Cu-BTC/Cu2O film was prepared on the copper surface by in-situ synthesis method, and it was further hydrophobically modified by POTS with low surface energy to give Cu-based MOF superhydrophobic film for the corrosion protection performance investigation in simulated seawater. One advantage of this experiment is that the synthesis method Cu-BTC film is green and environmentally friendly, in which Cu matrix is directly used to replace Cu salt in the reaction to reduce the threat of environmental pollution. CuO/Cu2O bilayer film was prepared by heat treatment of copper substrate in air atmosphere, and then it further hydrothermally reacted with 1,3,5-benzenetricarboxylic acid (H3BTC) in water/ethanol solution to obtain Cu-BTC film. Scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray electron spectroscopy (XPS) and Fourier infrared transform spectroscopy (FTIR) etc. were used to characterize the prepared surfaces, which proved the successful preparation of Cu-BTC MOF film. The surface wettability of copper substrate before and after treatment was compared by water contact angle test, and the optimized superhydrophobic surface showed a high water contact angle of 165.2°. The self-cleaning and anti-corrosion properties of the prepared superhydrophobic surface were tested, and the results showed that the in-situ prepared MOF superhydrophobic film possessed not only satisfactory self-cleaning property, but also good protection against copper corrosion. This work could provide new ideas and some guidance for the development of more green and environment-friendly superhydrophobic anti-corrosion surfaces.

In summary, this dissertation expands the application scope of MOFs, especially in the field of marine science, provides a new thought for the preparation of high sensitivity to detect corrosion electrochemical sensing platform, extends new materials and new technologies for preparing superhydrophobic surfaces and coatings. It demonstrates the promising application potential of the stable superhydrophobic coating in the field of marine corrosion protection, and has important value to deepen the MOFs application in the wider research fields.

Subject Area海洋科学
MOST Discipline Catalogue理学::海洋科学
Language中文
Document Type学位论文
Identifierhttp://ir.qdio.ac.cn/handle/337002/156808
Collection海洋环境腐蚀与与生物污损重点实验室
Recommended Citation
GB/T 7714
陈怀银. 金属有机骨架材料在海洋腐蚀检测与防护中的应用研究[D]. 中国科学院海洋研究所. 中国科学院大学,2019.
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