【作者】 赵娣芳；

【导师】 刘宁； 周杰；

【作者基本信息】 合肥工业大学 ， 材料学， 2006， 博士

【摘要】 本文应用粘土矿物学、胶体与表面化学、吸附作用应用原理及抗菌试验方法研究了金属离子对天然粘土矿物—坡缕石的改性及其所产生的抗菌性能，同时对光催化材料纳米二氧化钛的固定化方法进行了研究，在此基础上制备了基于坡缕石载体的金属离子—光催化型纳米复合无机抗菌剂，并对该抗菌剂进行了结构表征及性能测试。 首先，介绍了无机抗菌剂的产生、发展、性能、分类、抗菌机理、研究现状、存在的问题以及坡缕石的发展应用前景，并介绍了半导体材料纳米氧化钛抗菌自洁材料的光催化作用原理、提高光催化效率的方法。重点概述了金属离子型无机抗菌剂的活性组份、载体、抗菌机理及评价指标。指出了金属离子型无机抗菌剂研发中存在的问题。提出以我国储量丰富的世界稀有的天然一维纳米材料—坡缕石作为无机抗菌剂的载体，以价廉的铜离子作为抗菌活性组份的设想。对天然坡缕石进行了提纯和活化处理，并采用Ag⁺、Cu²⁺对坡缕石进行了离子交换性改性，对提纯、活化和改性工艺进行了参数优化实验，得到了纯度高，分散性好、表面活性高的活化坡缕石以及负载一定量的金属离子型坡缕石无机抗菌剂。研究发现，天然矿物中坡缕石和蒙脱石不易分离，而其他非粘土类杂质可被完全去除。坡缕石上负载金属离子量的多少主要受到坡缕石自身的晶体结构、表面特性等因素影响较大，其负载量达到一定限度时即不易再提高。 其次，对金属离子型坡缕石和以坡缕石为载体的金属离子—光催化型纳米复合无机抗菌剂的微观形貌、晶体结构和表面特性进行了研究，对Ag⁺、Cu²⁺改性坡缕石的XRD和TEM的观察和分析认为，该种类型无机抗菌剂基本保持了坡缕石原来的微观形貌、晶体结构特征和吸附特性。分别采用中和水解法和溶胶—凝胶法制备了以坡缕石为载体的金属离子—光催化型纳米复合无机抗菌剂，实验结果证明：该复合粉体实现了纤维状矿物材料和纳米氧化钛粒子的1—0维的纳米复合，保证了各组成相始终高度分散，得到了光催化性能良好的粒度极为细小的锐钛矿型纳米氧化钛。XPS光电子能谱实验结果表明：纳米氧化钛和坡缕石之间实现了Si-O-Ti的化学键连结构，保证了纳米氧化钛分子牢固附着在坡缕石的表面，而充分发挥二者的纳米效应。 再次，对金属离子型坡缕石和基于坡缕石载体的金属离子—光催化型纳米复合无机抗菌剂的抗菌性能、缓释性能、变色性、吸附降解有机物的性能等进行了研究。针对单纯金属离子型无机抗菌剂虽然能够杀灭或抑制细菌的生长，但不能实现自洁功能的状况，将纳米氧化钛的光催化降解有机物的功能与离子型无机抗菌剂实现复合。可减少使用中的添加量，节省成本，同时该复合抗菌剂一方面可使金属离子型和光催化型二者协同抗菌，另一方面由于金属离子的掺杂作用，使纳米氧化钛的光催化效率得到了极大提高，使纳米氧化钛抗菌自洁材更多还原

【Abstract】 Preparation, structural characterization and properties test of the cationic-photocatalytic nanocomposite inorganic antibacterial agent based on palygorskite carrier on the basis of the research on the technics and antibacterial properties of palygorskite natural clay mineral modified by metal ions and the methods of the fixed nanoTiO₂ photocatalytic material preparation by application of clay mineralogy, colloid and interface chemistry and adsorption application theory.In the first part, the creation, development process, property, classification, mechanism of antibacteria, study present state, questions and the perspectives of palygorskite application of inorganic antibacterial agent as well as the photocatalysis theory of semiconductor nanoTiO₂ self purification antibacteial material have been outlined. A special attention is paid to the active component, carrier, antibacterial mechanism and assessment index mark of inorganic antibacterial agent. Simultaneously, the problem in present research progress is pointed out. The envisage of preparing the inorganic material which take the palygorskite—a type of natural one-dimentional nanometer clay material abundant in our country and rare in the world as carrier and the bargain Cu²⁺ as active component is put forward. The treatment of purification and activation to natural palygorskite is adopted and the purified palygorskite is modified with Ag+ and Cu2+ by the method of liquid ion exchange. The parameters of preparing the samples are optimized. The purified palygorskite and activated palygorskite which has high percentage purity, good dispersibility and high surface activity are obtained as well as a type of metal ionic palygorskite antibacterial inorganic agent which carrying a given of metal ion. The study has discovered that the palygorskite and montmorillonite in natural palygorskite was not easy to seperation however the other non-clay mineral impurities can be discarded altogether. The metal ion supported by palygorskite is severe effected by the crystal structure, surface properties of palygorskite itself and the amount of metal ion can not be increased when it reach a certain level.In the second part, the microgragh, crystal structure and surface properties of cationic palygorskite and cationic-photocatalytic nanocomposite inorganic antibacterial agent based on palygorskite carrier have been researched. The cationic palygorskite inorganic antibacterial agent preserved the microgragh, crystal structure and adsorption of original palygorskite basically. Preparation the cationic-photocatalytic nanocomposite inorganic antibacterial agent based on palygorskite carrer by the method of counteraction hydrolysis and sol-gel, respectively. The experiment confirmed that the nanocomposite powder is implementation the procedure of one-dimentional fibrous clay mineral recombination to the 0-dimentional nanometer TiO₂ particles, and it assurance the good dispersibility of every build-up phase. The TiO₂ particle is anatase and the grain is very fineness.更多还原