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BiOI基半导体薄膜材料的制备及其光催化防污性能研究
龙洋
学位类型硕士
导师张盾
2017-05-10
学位授予单位中国科学院大学
学位授予地点北京
学位专业海洋腐蚀与防护
关键词生物污损 Bioi 半导体薄膜 防污材料 光催化杀菌机理 Marine Biofouling Semiconductor Film Antifouling Materials Photocatalytic Antibacterial Mechanism
摘要海洋生物污损影响海洋工程材料的正常服役,是人类开发利用海洋难以回避的问题。因此,研发新型、高效、环保防污材料具有重要的现实意义。光催化防污技术以其低能耗、环境友好等优点受到越来越多的关注。为克服传统光催化材料(如TiO2)对太阳能利用效率低以及光催化粉体材料回收难等缺点,本论文以BiOI可见光催化半导体材料为研究对象,发展了在常温常压下具有纳米分级结构四方相BiOI单体材料的简易制备方法。在此基础上采用原位生长技术实现了BiOI在金属基体上的薄膜化,并进一步采用离子交换法将BiOI单体薄膜加以改性制得BiOI/BiOBr二元半导体复合薄膜材料。具体研内容如下:
(1)通过控制共沉淀反应条件,在常温常压不添加表面活性剂的条件下实现了具有花球状分级结构BiOI单体纳米材料的可控合成。在可见光激发下,实现了对污损细菌的高效杀灭。杀菌机理研究表明:h+和·O2-自由基的产生致使细菌细胞壁膜的破坏是BiOI在水体环境中保持高效光催化杀菌性能的根本原因。
(2)利用无机晶体原位生长技术,首次实现了在金属基体(304SS)表面构建具有良好光催化活性的BiOI薄膜。优化各制备工艺参数后,在140 oC,PVP为 0.10 g,反应时间为4 h条件下,制备了物理结构及光化学性质稳定性最佳的BiOI薄膜材料。薄膜呈纳米分级结构,均匀覆盖于金属基体表面,其光催化活性与BiOI粉体材料相比无明显下降。对海洋污损模式细菌及污损藻类显示出良好的光催化杀灭及防附着性能。
(3)以四丁基溴化铵(TBAB)为溴源,采用离子交换方法,在304SS基体表面成功构筑了具有p-n异质结结构的BiOI/BiOBr二元复合半导体薄膜材料,与BiOI单体薄膜材料相比其光催化活性明显提高。此外,研究证实了其对细菌胞质内遗传物质(环状质粒DNA)具有光催化开环破坏作用,进一步丰富了光催化材料的杀菌防污机理。
其他摘要Marine biofouling affects the normal use of marine engineering materials, which is a difficult issue for human exploitation of the oceans. Therefore, the design and development of new, efficient and environmental friendly antifouling materials is of practical significance. Photocatalytic antifouling technology with its own low energy consumption and environmental friendly advantages attracts more and more attention. In order to overcome the low solar energy utilization of the traditional photocatalytic materials (such as TiO2) and the hardness recovery processes of photocatalytic powder materials. In this thesis, the visible light response BiOI semiconductor material has been studied. BiOI with hierarchical structure has been synthesized by an easy way under the room temperature. On the basis of that, by using in situ growth method, the BiOI nanostructure film has been successfully fabricated on 304 stainless steel (304SS) substrates and by further using ion-exchange method, the construction of BiOI/BiOBr binary composite film materials has been achieved. Specific research contents are as follows:
(1) By controlling coprecipitation conditions, the spherical hierarchical BiOI has been synthesized at room temperature. Under the visible light, the hierarchical structure BiOI demonstrates efficient bactericidal properties. The study of the sterilization mechanism shown that h+ and ·O2- free radicals which damage the bacterial cell wall and membrane is the basic reasons for the efficient sterilization of BiOI under the visible light irradiation. 
(2) The BiOI nanostructure film has been successfully fabricated on 304SS substrates using in situ growth method for the first time. The best physical stability and photochemical properties of BiOI nanostructure film has been prepared by hydrothermal reaction under 140 oC, PVP 0.10 g for 4 hours. The hierarchical nanostructure BiOI film covered the metal surface and its photocatalytic activity does not declined significantly compared to the BiOI powder materials. Therefore it possesses a good photocatalytic disinfection activity for both marine fouling bacteria and algae.
(3) BiOI/BiOBr binary composite thin film materials have been successfully fabricated on 304SS surface by the ion-exchange method using TBAB. Compared with the BiOI nanostructure film, the photocatalytic activity of the BiOI/BiOBr binary composite film is strengthen for the p-n heterojunction accelerating the separation of the photo-induced electron-hole pairs. Moreover, the bactericidal mechanism of this binary composite film has also been further enriched by its photocatalytic degradation of bacterial plasmid, the genetic material in the bacterial cells.
学科领域海洋化学
语种中文
文献类型学位论文
条目标识符http://ir.qdio.ac.cn/handle/337002/136606
专题海洋腐蚀与防护研究发展中心
作者单位中国科学院海洋研究所
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龙洋. BiOI基半导体薄膜材料的制备及其光催化防污性能研究[D]. 北京. 中国科学院大学,2017.
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