磁性有序中孔碳对水中抗生素类药物的吸附机理和构效关系研究

With the widespread application of antibiotics and other antimicrobic agents, the residuals and potential hazards in both natural and human environment have raised public concerns and demand effective control. Ordered mesoporous carbon (OMC) has received considerable attention in environmental pollution control due to its highly ordered and well-controlled mesoporous structures. Its unique pore structure provides advantages for the transfer and adsorption of contaminants, especially for bulky organic compounds. However, the adsorption mechanism and correlation between structures and adsorption capacities of OMC are not clear enough till now. Meanwhile, as the nano-adsorbents, it is difficult to be separated from solution. The present project aims to systematically study the adsorption mechanism and structure-activity relationship of typical antibiotic chemicals (sulfamethoxazole, tetracycline and tylosin) on surface-functional magnetic OMC with varied pore structures, which is easy to be separated by external magnetic. The influence of pore structure of adsorbent (size, ordered and shape), antibiotic molecular size and water chemistry (time, pH and temperature) on adsorption behaviors will be systematically investigated by using batch technique, advanced characterization techniques and computational calculation. The adsorption mechanism will be elucidated, and the relationship between the structure and surface chemical characteristics of magnetic OMC and the efficiency for antibotics adsorption will be estblished. This project will provide the theoretical basis and technical supports for the efficient removal of antibiotics in natural environment.

抗生素类药物滥用所造成的水环境污染问题日趋严重，亟待进行有效治理。中孔碳因其发达的适于大分子扩散的中孔通道而被广泛应用于抗生素类药物的去除，但吸附机理和构效关系尚不明确，且难分离回收。本项目拟以具有高吸附及磁分离性能的磁性有序中孔碳为吸附剂，以磺胺、四环素和泰乐菌素等抗生素作为研究对象，采用静态吸附法、微观表征技术并结合理论计算从宏观和微观两方面系统研究磁性中孔碳的孔道（大小、有序、形状等）和表面（酸碱性、磁性等）特性、抗生素分子（尺寸、电子结构等）及水化学条件（时间、pH和温度等）对吸附的影响，在分子水平上解析阐明抗生素在磁性有序中孔碳上的吸附作用机制，揭示磁性有序中孔碳的孔道和表面特性与其吸附性能间的构效关系。项目预期成果将为水中抗生素类药物的高效去除提供理论依据和技术支撑。

能源危机和环境污染是当今社会面临的两大难题，吸附和催化是解决能源短缺及环境污染问题的潜在两大技术。构建高效、快速去除水中污染物的功能型吸附材料一直水污染治理方面的核心课题之一。另一方面，光生电荷能否有效分离将决定光吸收的提高和表面特性的调控是否能达到提髙光催化活性的目的。因此，对光生电荷分离效率的研究将有助于打破该瓶颈．实现光催化效率的本质提升。因此，在本项目的资助下，主要进行两大方面的研究，具体如下：.1）基于先进复合材料应用于染料、抗生素及其复合污染物的去除。主要内容如下：.A：制备高比表面积的2D/3D MgSiO/碳空心球复合材料，用于四环素和铀复合污染的去除。.B：基于介孔碳的高吸附性，开发一种磷化钴修饰介孔碳活化PMS降解有机污染物的技术，实现了对四环素的降解和吸附。.C：以三种钴铝层状双氢氧化物为模型，研究了二维和三维材料（实心/空心）的结构与吸附性能的关系。.2）性能导向的功能微纳材料设计及其在光催化制氢和催化降解有机污染物领域的研究。主要内容如下：.A：通过双重缺陷策略制造了一个直接的Z型制氢系统。优化的双缺陷复合材料的析氢速率约为651.79μmol/h，周转频率约为419.3 h-1，并且具有高稳定性。.B：六次甲基四胺活化制备三维层状碳掺杂g-C3N4纳米片光催化剂。优化后的材料在420 nm处实现了高达7.8%的量子效率，其H2释放速率> 2.7×104 μmol/g/h，是原始g-C3N4的31.3倍。.C：通过带负电的2D超薄ZnIn2S4纳米片和2D质子化的g-C3N4纳米片之间的静电自组装策略，制备了2D/2D ZnIn2S4/pCN复合材料。优化后的复合材料在可见光下的析氢速率高达~8601.16μmol/g/h。.D：静电自组装法合成2D/3D Z-scheme Ni(OH)2/g-C3N4及其光催化析氢性能研究。优化后的复合材料析氢速率是纯g-C3N4析氢速率的76倍。.E：制备g-C3N4纳米片-Co3O4 量子点2D/0D异质结构，提供丰富的活性位点和有效的界面接触，构建有效的电荷传输途径，改善PMS活化性能，实现四环素的高效降解。.F：超薄g-C3N4/非晶态Cu掺杂FeOOH纳米团簇的制备及其光-芬顿性能研究。.上述合成的高活性功能材料，对环境有机污染物的治理和光催化制氢具有一定的现实意义。