多级复合孔复杂中空结构的可控合成及其构效关系
发布时间：2018-11-05 08:17
【摘要】：本文主要合成了三种不同材料的具有多级复合孔的复杂中空结构,即多壳或多核结构。由于结构上的特殊性和性能上的优越性,具有不同内部核壳结构的微纳米材料越来越多地受到人们的关注。这种结构的材料通常具有较低的密度,较大的比表面积,较高的负载量和催化效率,并且可以有效地缩短物质或电荷传输过程的路径,因而在微尺度反应器、药物载体等许多领域都有重要的应用前景。然而目前来说,对于具有复杂内部核壳结构的中空微纳米材料的可控合成仍然是一大挑战。另一方面,一种新型的多孔材料——多级复合孔材料,随着多孔材料的发展而逐渐产生。它不同于单一孔径的多孔材料,这种复合孔材料具有两种或两种以上不同孔径的孔结构,并且按孔径逐级分布。这样的结构既可以保证产物有较大的比表面积和活性位点,又有助于物质的传递,减少物质扩散过程中所受到的阻力。故而它的各方面性能优越,逐渐受到研究者的青睐。但是同时具备多级复合孔和不同内部核壳结构的微纳米材料尚未见报道。本论文基于目前的研究现状和研究趋势,以合成同时具有多级复合孔和多壳或多核内部结构的微纳米材料为研究目标,着重利用模板法合成具有多级复合孔的多壳/核结构的微纳米材料,对产物用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、扫描透射电镜(STEM)等手段进行表征,并探讨它们在相关应用方面的性能。进一步地,我们对产物的生成机理进行了阐述,以此指导其他类似结构产物的合成,为其他材料的合成提供借鉴。本论文主要开展了以下几项工作:(1)可控合成了具有多级复合孔的不同壳层的Zn O中空材料,并研究了其形成机理和光催化性能。采用简化模板法,分别可控合成了具有多级复合孔的单层、双层和三层的Zn O中空材料。通过对产物的表征,确定了它们的大小、形貌及内部结构;通过对合成过程的实时监测,提出了温度梯度形成机理;并研究了产物在光催化方面的性能,表明随着壳层数的增加,Zn O对Rh B的催化降解性能和催化剂的循环效率都随之提高,在水处理方面表现出良好的应用前景。尤其是产物形成机理的研究,有助于指导类似结构产物的合成,从而更好的控制合成具有不同内部结构的中空微纳米材料。(2)可控合成了具有多级复合孔结构的多壳Ca CO3中空材料,并分析了产物的形成机理。我们巧妙利用有机酸钙的热分解,并通过对反应条件的调整,实现了对产物形貌的有效调控,得到了具有多级复合孔结构的单层、双层和三层Ca CO3中空材料。采用多种测试手段对样品进行表征分析,确定了产物的相关结构及性质;通过对反应过程的监测和分析,我们认为不同结构产物的形成依赖于模板层层加热机理。多层Ca CO3属于氧化物之外的多层壳材料,丰富了多层壳材料的种类,为其他类似结构碳酸盐材料的合成提供了借鉴。(3)探讨了所合成的具有多级复合孔的三层结构碳酸钙(记为HPTHMs)在作为p H响应性抗癌药物载体方面的性能。我们将HPTHMs应用于抗癌药物盐酸阿霉素(DOX-HCl)的负载和不同p H条件下的释放实验。结果表明,HPTHMs作为药物载体,具有较高的药物吸附效率和负载量,并且对药物呈现良好的p H响应性释放;通过流式细胞术(FCM)、激光共聚焦显微分析(CLSM)等手段证明了载体的存在,提高了癌细胞对DOX的摄入,增强了抗癌效果;体内/外实验进一步证明载药后的HPTHMs-DOX样品对癌细胞和肿瘤组织的生长都有较好的抑制作用。可以看到,HPTHMs在响应性抗癌药物运输方面具有良好的应用前景。(4)合成了具有多级复合孔的多核结构La2O2CO3材料,并初步探讨了产物的生成机理。采用模板法,并利用醋酸镧盐的热分解,得到了具有多级复合孔和不同核数的多核结构La2O2CO3材料。通过一系列的表征观察了产物的形貌及多孔结构;并通过中间产物的存在对其形成机理进行了初步探讨,当然确切的机理仍需要更多的实验数据证明。多孔以及多核结构的存在,有利于La2O2CO3与磷酸盐的接触,提高对磷酸盐的沉淀效率,为其作为高效的磷酸盐结合剂提供可能。
[Abstract]:In this paper, three complex hollow structures with multi-stage composite pores, i.e. multi-shell or multi-core structures, are synthesized. Due to the particularity and superiority of structure, micro-materials with different internal core shell structures have been paid more and more attention. The material of this structure usually has lower density, larger specific surface area, higher loading and catalytic efficiency, and can effectively shorten the path of substance or charge transfer process, and has important application prospect in many fields such as micro-scale reactor and drug carrier. At present, however, the controllable synthesis of hollow micro-materials with complex internal core shell structures remains a challenge. On the other hand, a new porous material _ multi-stage composite pore material is gradually developed with the development of porous material. which is different from the porous material of a single pore size, and the composite pore material has two or more pore structures with different pore sizes, and is distributed in a step by step according to the pore size. Such a structure can ensure that the product has a larger specific surface area and an active site, but also contributes to the transfer of substances and reduces the resistance to substance diffusion. So its aspects are superior and gradually favored by researchers. However, micro-materials with multi-stage composite pores and different internal core shell structures have not been reported. Based on current research situation and trend of research, this paper aims at synthesizing micro-nano material with multi-stage composite pore and multi-shell or multi-core internal structure at the same time, and mainly uses template method to synthesize micro-nano material with multi-shell/ core structure with multi-stage composite pores, The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), scanning electron microscope (STEM), etc. Further, we set forth the mechanism of product formation, so as to guide the synthesis of other similar structure products and provide reference for the synthesis of other materials. The paper mainly carries out the following work: (1) Controllable synthesis of Zn O hollow materials with different shell layers with multi-stage composite pores, and studies its formation mechanism and photocatalytic performance. By adopting the simplified template method, a single layer, a double layer and a three-layer Zn O hollow material with a multi-stage composite pore are respectively controlled and synthesized. Through the characterization of the product, the size, morphology and internal structure of the product are determined. Through real-time monitoring of the synthesis process, the forming mechanism of the temperature gradient is put forward, and the performance of the product in photocatalysis is studied, indicating that with the increase of the number of layers of the shell, The catalytic degradation performance of the Zn O to Rh B and the cycle efficiency of the catalyst are improved, and a good application prospect is shown in the water treatment. In particular, the research on the formation mechanism of products helps to guide the synthesis of similar structural products, so as to better control the synthesis of hollow micro-materials with different internal structures. (2) a multi-shell Ca-CO3 hollow material with multi-stage composite pore structure is synthesized and the formation mechanism of the product is analyzed. We skillfully utilize the thermal decomposition of organic acid calcium, and through the adjustment of the reaction conditions, the effective regulation of the product morphology is realized, and a single layer, a double layer and a three-layer Ca CO3 hollow material with a multi-stage composite pore structure are obtained. The structure and properties of the product are determined by means of a variety of test methods. Through the monitoring and analysis of the reaction process, we believe that the formation of different structural products depends on the heating mechanism of the template layer. The multi-layer CaCO3 belongs to the multi-layer shell material other than the oxide, enriches the variety of the multi-layer shell material and provides a reference for the synthesis of other similar structural carbonate materials. (3) The properties of the synthesized three-layer structure calcium carbonate (HPTHMs) with multi-stage composite pore were discussed. We applied HPTHMs to the loading of anti-cancer drug hydrochloride (DOX-HCl) and release experiments under different p-H conditions. The results show that HPTHMs can be used as drug carrier, have higher drug adsorption efficiency and loading capacity, and have good p-H response release on drug; by flow cytometry (FCM) and laser confocal microscopy (CLSM), the existence of vector is proved. The uptake of DOX by cancer cells is improved, and the anti-cancer effect is enhanced; and in vivo/ external experiments further prove that the HPTHMs-DOX sample after drug loading has good inhibiting effect on the growth of cancer cells and tumor tissues. It can be seen that HPTHMs have good application prospects in response to anti-cancer drug transport. (4) The multi-core La2O2CO3 material with multi-stage composite pores was synthesized, and the product formation mechanism was preliminarily discussed. A multi-core La2O2CO3 material with multi-stage composite pores and different cores was obtained by using template method and thermal decomposition of zinc acetate salt. The morphology and porous structure of the product are observed through a series of characterization, and the formation mechanism of the product is preliminarily discussed through the presence of intermediate products. The existence of porous and multi-core structures facilitates the contact of La2O2CO3 with phosphate, improves the precipitation efficiency of phosphate, and provides it as a high-efficiency phosphate binding agent.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.4
本文编号：2311476
[Abstract]:In this paper, three complex hollow structures with multi-stage composite pores, i.e. multi-shell or multi-core structures, are synthesized. Due to the particularity and superiority of structure, micro-materials with different internal core shell structures have been paid more and more attention. The material of this structure usually has lower density, larger specific surface area, higher loading and catalytic efficiency, and can effectively shorten the path of substance or charge transfer process, and has important application prospect in many fields such as micro-scale reactor and drug carrier. At present, however, the controllable synthesis of hollow micro-materials with complex internal core shell structures remains a challenge. On the other hand, a new porous material _ multi-stage composite pore material is gradually developed with the development of porous material. which is different from the porous material of a single pore size, and the composite pore material has two or more pore structures with different pore sizes, and is distributed in a step by step according to the pore size. Such a structure can ensure that the product has a larger specific surface area and an active site, but also contributes to the transfer of substances and reduces the resistance to substance diffusion. So its aspects are superior and gradually favored by researchers. However, micro-materials with multi-stage composite pores and different internal core shell structures have not been reported. Based on current research situation and trend of research, this paper aims at synthesizing micro-nano material with multi-stage composite pore and multi-shell or multi-core internal structure at the same time, and mainly uses template method to synthesize micro-nano material with multi-shell/ core structure with multi-stage composite pores, The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), scanning electron microscope (STEM), etc. Further, we set forth the mechanism of product formation, so as to guide the synthesis of other similar structure products and provide reference for the synthesis of other materials. The paper mainly carries out the following work: (1) Controllable synthesis of Zn O hollow materials with different shell layers with multi-stage composite pores, and studies its formation mechanism and photocatalytic performance. By adopting the simplified template method, a single layer, a double layer and a three-layer Zn O hollow material with a multi-stage composite pore are respectively controlled and synthesized. Through the characterization of the product, the size, morphology and internal structure of the product are determined. Through real-time monitoring of the synthesis process, the forming mechanism of the temperature gradient is put forward, and the performance of the product in photocatalysis is studied, indicating that with the increase of the number of layers of the shell, The catalytic degradation performance of the Zn O to Rh B and the cycle efficiency of the catalyst are improved, and a good application prospect is shown in the water treatment. In particular, the research on the formation mechanism of products helps to guide the synthesis of similar structural products, so as to better control the synthesis of hollow micro-materials with different internal structures. (2) a multi-shell Ca-CO3 hollow material with multi-stage composite pore structure is synthesized and the formation mechanism of the product is analyzed. We skillfully utilize the thermal decomposition of organic acid calcium, and through the adjustment of the reaction conditions, the effective regulation of the product morphology is realized, and a single layer, a double layer and a three-layer Ca CO3 hollow material with a multi-stage composite pore structure are obtained. The structure and properties of the product are determined by means of a variety of test methods. Through the monitoring and analysis of the reaction process, we believe that the formation of different structural products depends on the heating mechanism of the template layer. The multi-layer CaCO3 belongs to the multi-layer shell material other than the oxide, enriches the variety of the multi-layer shell material and provides a reference for the synthesis of other similar structural carbonate materials. (3) The properties of the synthesized three-layer structure calcium carbonate (HPTHMs) with multi-stage composite pore were discussed. We applied HPTHMs to the loading of anti-cancer drug hydrochloride (DOX-HCl) and release experiments under different p-H conditions. The results show that HPTHMs can be used as drug carrier, have higher drug adsorption efficiency and loading capacity, and have good p-H response release on drug; by flow cytometry (FCM) and laser confocal microscopy (CLSM), the existence of vector is proved. The uptake of DOX by cancer cells is improved, and the anti-cancer effect is enhanced; and in vivo/ external experiments further prove that the HPTHMs-DOX sample after drug loading has good inhibiting effect on the growth of cancer cells and tumor tissues. It can be seen that HPTHMs have good application prospects in response to anti-cancer drug transport. (4) The multi-core La2O2CO3 material with multi-stage composite pores was synthesized, and the product formation mechanism was preliminarily discussed. A multi-core La2O2CO3 material with multi-stage composite pores and different cores was obtained by using template method and thermal decomposition of zinc acetate salt. The morphology and porous structure of the product are observed through a series of characterization, and the formation mechanism of the product is preliminarily discussed through the presence of intermediate products. The existence of porous and multi-core structures facilitates the contact of La2O2CO3 with phosphate, improves the precipitation efficiency of phosphate, and provides it as a high-efficiency phosphate binding agent.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.4
【共引文献】
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2 刘永军;基于诊断治疗学多功能纳米系统用于肝细胞癌的分子诊断与治疗[D];山东大学;2014年
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