海洋环境腐蚀与生物污损重点实验室知识库

      海洋工程材料在服役时，生物污损是一个十分严峻的问题。因此，研发新型、 环保、高效的防污材料对于解决这一现实问题具有重要的意义。近年来，铋（Bi） 系纳米材料及其复合材料因其优异的可见光吸收性能和光催化活性，在光催化防 污方面已经被证明具有应用前景。但是在实际防污应用中，Bi 系光催化材料主要 采用粉末，而粉末材料存在回收过程复杂等缺点。因此，有必要将 Bi 系纳米材 料固定在基板上以提高可回收性。分析前人研究，本研究对现有 Bi 系光催化薄 膜制备工艺较复杂、载体材料成本较高和应用环境局限等瓶颈问题，基于聚合物 结构优势，可控原位生长聚合物基 Bi 系光催化薄膜，进一步拓宽光催化薄膜的 制备技术和应用范围。研究不同聚合物结构表面 Bi 系薄膜的原位生长，揭示薄 膜原位生长机制，建立聚合物表面能或官能团与薄膜生长之间的构筑关系。通过 原位生长温度和时间等调控合成不同形貌结构和化学成分的铋系薄膜，明确薄膜 的生长影响控制因素。以降解有机污染物和杀灭细菌评价薄膜的催化性能，探究 薄膜的防污功效。3D 打印技术定制大比表面积聚合物载体结构，助力光催化薄 膜的实际应用。具体内容如下：

       1. 水热法在聚氯乙烯（PVC）聚合物表面制备 Bi 系薄膜，Bi 薄膜的生长与 水热合成温度和时间有关，与聚乙烯吡咯烷酮（PVP）含量无关。在水热环境下， PVC 表面氯原子的脱附造成表面电荷不稳定，诱导溶液中 O 和 Bi 元素吸附生成 Bi₂O_2.7 和 Bi₂O₃。高温高压环境下易诱导形成 Bi₂O₃ 的前驱相 Bi₂O_2.7。140℃水热 环境下原位生长 4 h 获得 0.81 μm 厚的 Bi 系 p−n 异质结薄膜。该研究为首次使 用聚合物作为载体材料在水热环境成功制备 Bi 系薄膜的成功实例。使用沉淀还 原法在薄膜表面负载等离子体共振 Ag 纳米粒子能够明显提高薄膜的可见光吸收 性能。Ag/Bi₂O₃/Bi₂O_2.7薄膜在可见光辐照下产生超氧自由基（·O₂⁻）和空穴（h⁺），Ag 纳米粒子为光生载流分离提供了条件并促进活性氧（ROS）的产生。薄膜对 罗丹明 B（RhB）溶液和大肠杆菌（E. coli）具有明显的降解和灭活活性。

       2. 采用水热法在 ER 等多种聚合物材料表面原位制备 Bi 系薄膜。研究发现 水热法原位制备 Bi 系薄膜对聚合物载体具有选择性。除 PVC 外，环氧树脂（ER） 表面能够水热原位生长 Bi 系薄膜。Bi 系薄膜的水热原位生长与聚合物材料表面 能无关，而与聚合物材料的官能团性质有关。ER 表面原位生长 Bi 系薄膜与水热 合成温度、时间和 PVP 含量都相关。在水热环境下，ER 的环氧基团与 PVP 的氨 基基团之间的偶极相互作用首先诱导 Bi³⁺在 ER 表面形成生长活性位点。随着溶 液中离子浓度的变化，逐渐诱导薄膜的自组装生长。在含有 0.1 g PVP 的 140℃ 水热环境下（70 mL 乙二醇和 10 mL 的蒸馏水）生长 2 h 获得 13 μm 厚的 Bi 系Z 型 Bi₂O₃/BiOI 异质结薄膜。沉淀还原法在薄膜表面负载表面等离子体共振 Ag 纳米粒子提高薄膜的可见光吸收性能。Ag/Bi₂O₃/BiOI 薄膜在可见光辐照下产生 ·O₂⁻和羟基自由基（·OH），Ag 纳米粒子为光生载流子的分离提供条件并促进 ROS 的产生。薄膜对三氯生（TCS）和 RhB 溶液以及 E. coli 和金黄色葡萄球菌（S. aureus）具有明显的降解和灭活效率，并对假交替单胞菌（Pseudoalteromonas sp.） 具有一定的抗粘附性。薄膜展现出良好的光催化活性循环稳定性。

       3. 通过简单易行的浸涂法在室温和常压下于聚合物基材表面原位制备碘缺 陷 BiOI 薄膜。浸涂法能够在各种聚合物构筑 Bi 系薄膜，对聚合物载体材料无选 择性。在薄膜制备过程中，首先通过 Bi³⁺在聚合物基材表面吸附形成薄膜生长活 性位点。随着提拉原位生长时间的延长，薄膜逐渐自组装为花瓣状 BiOI 薄膜。 高比例的和运动的 I⁻促进 BiOI 薄膜沿（110）晶面生长。在薄膜的生长过程中， 通过 NaOH 调节碘化钾（KI）溶液的 pH，OH⁻和碘原子发生置换作用，碘空位 被引入到 BiOI 晶体中，导致 BiOI 内部电场和电子密度增强，有效地提高了 BiOI 的光生载流子的分离和传输效率。碘缺陷 BiOI 相对于化学计量比 BiOI 展现出更 小的晶粒尺寸、更高的比表面积、电负性和光电响应，碘缺陷 BiOI 展现出更高 的光催化活性。在初始混合溶液下，调节溶液 pH 6~9 原位制备的薄膜为 BiOI/I 缺陷 BiOI Z 型异质结结构，该薄膜在可见光辐照下同时产生·O₂⁻，·OH 和 h ⁺， 薄膜对 RhB 溶液和 E. coli 具有降解和灭活效率。

        4．通过 3D 打印技术设计大比表面积聚合物载体结构和改进光源辐照系统， 简单易行的浸涂法在 3D 打印类碳纳米管（CNT）和 MOF 结构表面原位提拉制 备碘缺陷 BiOI 薄膜。改进的光源辐照系统有效地提高了薄膜的光催化效率。在 初始混合溶液下，调节溶液 pH 6~9 在类 CNT 聚合物结构载体表面原位提拉制备 BiOI/I 缺陷 BiOI Z 型异质结薄膜，该薄膜在可见光辐照下对 RhB 溶液、E. coli 和 S. aureus 具有高效的降解和灭活性能。

        Biofouling is one of the major problems faced by marine engineering materials in service. It is of great practical significance to develop new, environmental and efficient antifouling materials. In recent years, Bi based nanomaterials and their composites have been proved to be promising in the field of photocatalytic antifouling due to the excellent visible light absorption and photocatalytic activity. However, in practical applications, Bi-based photocatalytic materials are mainly applied in the form of powder, powdered materials have shortcoming with complicated recovery process, which limits its further application. Therefore, it is necessary to fix Bi-based nanomaterials on substrates to improve the recyclability. Analyzing the research of predecessors, this study can expand the preparation technology and application range of Bi-based photocatalytic films by constructing the Bi-based materials on polymer to solve the bottleneck problems of the existing film construction methods, such as complex preparation process, high cost of carrier materials and limited application environment. The films on different polymers are studied to reveal the films grown mechanism. Bi-based films with different morphologies, structures and chemical compositions are synthesized by adjusting the in-situ grown temperature and time. The photocatalytic performance of the film is evaluated by degrading organic pollutants and killing microorganism. Customized 3D printing large specific surface area polymer carriers are applied to facilitate the practical application of the photocatalytic film. The details are as follows:

     1. Hydrothermal in-situ grown Bi-based film is constructed on polyvinyl chloride (PVC). The in-situ grown Bi-based film is related to the hydrothermal temperature and time, but is not related to polyvinyl pyrrolidone (PVP) amount. In hydrothermal progress, the desorption of chlorine atoms on PVC causes surface charge instability and induces the adsorption of O and Bi elements to form Bi₂O_2.7 and Bi₂O₃. The Bi₂O_2.7 is the precursor phase of Bi₂O₃. 0.81 μm of Bi₂O₃/Bi₂O_2.7 p−n scheme heterostructure film fabricated at 140 ^oC for 4 h. This is the first successful example of using polymer as supported substrate to prepare hydrothermal Bi-based film. Furthermore, by using precipitation-reduction method, plasmon resonance Ag nanoparticles on film can obviously improve the visible light absorption performance of the film. Ag/Bi₂O₃/ Bi₂O_2.7 film produces ·O₂⁻ and h⁺ under the visible light irradiation. The film shows obvious degradation and inactivation activity to RhB and E. coli.

    2. Hydrothermal in-situ grown Bi-based film is constructed on epoxy resin (ER) and other polymer materials. It is found that Bi-based film prepared by hydrothermal method is selective to polymer substrates. The hydrothermal _in-situ grown of Bi-based film has nothing to do with the surface energy of polymer, but is related to the properties of polymer functional group. In addition to PVC, Bi-based film can be constructed on ER. In-situ grown Bi based films on ER is related to hydrothermal temperature, time and PVP amount. In hydrothermal progress, the dipole interaction between the epoxy group of ER and the amino group of PVP firstly induces Bi³⁺ to form the grown active sites on ER. With the amount change of Bi³⁺, O₂⁻ and I⁻ , the self-assembled grown of the film is gradually induced. 13 μm of B_i2O₃/ BiOI Z-scheme heterostructure film is fabricated at 140 ^oC with 0.1 g of PVP (70 mL glycol and 10 mL distilled water) for 4 h. The surface plasmon resonance Ag nanoparticles loaded on the film by precipitationreduction method can obviously improve the visible light absorption performance of the film. Ag/Bi₂O₃/BiOI Z-scheme heterostructure film produces ·O₂⁻ and ·OH under visible light irradiation. The film has obvious degradation and inactivation efficiency towards TCS, RhB, E. coli and S. aureus, and also has the significant anti-adhesion effect toward Pseudoalteromonas sp. The film shows good photocatalytic activity and cycle stability.

     3. SILAR in-situ grown BiOI film is constructed on polymers at room temperature and abnormal pressure. The SILAR method can construct Bi-based film on various polymers and has no selectivity for polymers. In SILAR process, Bi3+ firstly adsorbs on polymers to construct the active grown sites of the film. With the extension of time, the films gradually are self-assembled into petal-like BiOI film. High proportion and movement speed of I⁻ promote the in-situ grown of BiOI film along the (110) crystal plane. In the grown process of films, displacement function between OH⁻ and iodine atom occurs by adding NaOH to KI solution. Iodine spaces are introduced into the BiOI crystals, causing BiOI internal electric field and electron density increase and improve the photoinduced carrier separation and transmission efficiency. Iodine defects engineering BiOI exhibits smaller grain size, higher specific surface area, electronegativity, photoelectric response and photocatalytic activity than stoichiometry BiOI. The film fabricated at pH 6~9 is BiOI/I-defects engineering BiOI Z-scheme heterostructure can produce ·O₂⁻ , ·OH and h⁺, the film shows good degradation and inactivation efficiency towards RhB and E. coli.

    4. 3D-printing technology is introduced to design the polymer substrates with large specific surface area. I-defects engineering BiOI film is fabricated on 3D-printing model-like CNT and MOF substrates at pH 6~9 by SILAR method. The photocatalytic efficiency of the film is improved by the improved light source irradiation system. The film shows good degradation and inactivation towards RhB, E. coli and S. aureus.

第1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 典型海洋污损生物形成过程    2
1.1.3 海洋生物污损防护措施    3
1.2 光催化杀菌防污材料    7
1.2.1 半导体光催化杀菌技术    7
1.2.2 半导体光催化杀菌防污机理    8
1.3 铋系半导体光催化材料    11
1.3.1 铋系光催化材料的发展    11
1.3.2 铋系光催化薄膜的制备    15
1.4 选题依据和研究思路    18
1.4.1 选题依据    18
1.4.2 研究目标与内容    19
1.4.3 研究方案    20
第2章 聚合物PVC表面Ag/Bi2O3/Bi2O2.7 p-n型异质结薄膜的水热法可控构筑及其光催化机制研究    23
2.1 引言    23
2.2 实验部分    24
2.2.1 实验材料和试剂    24
2.2.2 实验用仪器    24
2.2.3 薄膜的水热法制备    25
2.2.4 薄膜的自清洁性能评估    26
2.2.5 薄膜的抗菌性能测试    26
2.2.6 薄膜光催化机制探究    27
2.3 结果与讨论    27
2.3.1 薄膜的结构和形貌    27
2.3.2 薄膜的自清洁性能分析    34
2.3.3 薄膜的杀菌和抗粘附性能分析    35
2.3.4 薄膜的光学性能和ROS测试分析    38
2.3.5 薄膜的光催化机制分析    39
2.4 小结    41
第3章 聚合物ER表面Ag/Bi2O3/BiOI Z型异质结薄膜的水热法可控构筑及其光催化机制研究    43
3.1 引言    43
3.2 实验部分    44
3.2.1 实验材料和试剂    44
3.2.2 薄膜的制备    44
3.2.3 实验用仪器    44
3.2.4 薄膜RhB和TCS降解性能评估    44
3.2.5 薄膜杀菌和抗菌粘附性能评估    45
3.3 结果和讨论    46
3.3.1 聚合物载体与Bi系薄膜水热原位构筑的关系性    46
3.3.2 薄膜的结构和形貌    47
3.3.3 薄膜的光学和自清洁性能分析    56
3.3.4 薄膜的杀菌性能分析    61
3.3.5 薄膜的光催化机理分析    64
3.3.6 TCS可能的光降解途径及产物的探索    66
3.4 小结    68
第4章 聚合物表面BiOI/I缺陷BiOI Z型异质结薄膜的浸涂法可控原位构筑及其机制研究    71
4.1 引言    71
4.2 实验部分    71
4.2.1 实验材料和试剂    71
4.2.2 薄膜的制备    72
4.2.3 BiOI粉末的制备    72
4.2.4 实验用仪器    73
4.2.5 薄膜和粉末光催化活性评估    73
4.2.6 密度泛函理论（DFT）计算    74
4.3 结果与讨论    74
4.3.1 薄膜的结构和形貌    74
4.3.2 碘缺陷BiOI粉末的结构    78
4.3.3 薄膜RhB降解性能分析    83
4.3.4 碘缺陷薄膜的杀菌性能分析    84
4.3.5 碘缺陷BiOI的光催化机理    84
4.4 小结    90
第5章 聚合物表面负载BiOI/I缺陷BiOI Z型异质结薄膜的3D反应器的设计和应用    91
5.1 引言    91
5.2 实验部分    91
5.2.1 实验材料和试剂    91
5.2.2 薄膜的制备    91
5.2.3 实验用仪器    92
5.2.4 辐照光源系统的改进    92
5.2.5 薄膜的光催化活性评估    93
5.3 结果与讨论    93
5.3.1 3D反应器的形貌    93
5.3.2 RhB降解性能分析    94
5.3.3 循环稳定性分析    95
5.3.4 杀菌性能分析    98
5.4 小结    101
第6章 结论与展望    103
6.1 结论    103
6.2 创新点    104
6.3 展望    105
附  录    121
致  谢    123
作者简历及攻读学位期间发表的学术论文与其他相关学术成果    125