Controllable Synthesis Of Porphyrin Nanomaterials Through Micro-emulsion Method

Nanomaterials has been drawn more and more attention because of its unique advantages and a wide application compared with traditional materials. Self-assembly technology is considered to be a significant method for the simple and efficient synthesis of nanomaterials. Supramolecular assembly method can effectively achieve the synthesis of porphyrin nanomaterials, while how to realize the control of porphyrin self-assembly is the key and difficult point. In order to get the discrete self-assembled porphyrin nanomaterials with well-defined shapes and sizes, the surfactant assisted self-assembly method is considered to be the most commonly used on the account of surfactant can encapsulate and slow-release of activated molecules. Micro-emulsion(?-emulsion) method that we developed previously to initiate self-assembly and formation of oil-soluble inorganic nanocrystals and tin(IV) meso-tetraphenyl porphyrin dichloride nanomaterials, it is expected to apply to self-assmbly of other tetraphenyl porphyrins. Due to the diversity of metal atoms in porphyrin center, the performance of porphyrin assemblies will also be different.Meanwhile, the introduction of new functional primitives such as inorganic nanocrystals in porphyrin self-assemble become an important research subject. The nanocomposites will collect superior properties of porphyrin and inorganic nanocrystals. The key point to implementing co-assembly lies in solving the problem of interfacial compatibility of each other. A novel and efficient method for inheriting and enhancing their individual functions is extremely desired. Based on the above mentioned background,our work mainly focuses on the following two aspects:1. By means of the method of interfacial self-assembly driven micro-emulsion process, we realized the controlled assembly of tetraphenyl manganese porphyrin(MnTPP). We obtained various hierarchical nanostructures such as polygon micrometer sheets, octahedra, and microspheres, by employing cationic surfactant(CTAB), anionic surfactant(SDS) and nonionic surfactant(P123). In order to study the influence of other factors such as concentration of porphyrin and surfactant, nucleation temperature, we carry out the research taking the synthesis of polygon micrometer sheets for example. In the process, we implement the control of shapes and sizes to porphyrin assembly. We peculated the pattern of aggregation and accumulation about porphyrin molecules, which were analyzed by Uv-vis, XRD and other testing methods.Finally, we observe changes of morphology and sizes obviously through the characterization of Dynamic light scattering(DLS), TEM and Uv-vis, thusing facilitating to understanding the process and mechanism of self-assembly.2. By selecting and designing reasonably interaction between building blocks and surfactant, it is possible to prompt co-assembly between porphyrins and inorganic nanocrystals. This chapter mainly includes two parts. Firstly, we accomplish the co-assembly between oil-soluble porphyrins and inorganic nanocrystals through Hydrophobic- hydrophobic interaction using the same method mentioned above. We got hybrid microspheres. Secondly, the gold NPs were initially stabilized by citrate ligands and subsequently coated with 4-Pyridine ethanethiol via ligand exchange, ZnTPyP/Au NPs nanocomposites were obtained by the stable coordination between nitrogen atom of the pyridine group and Zn atom in ZnTPyP which was the major drive force in the co-assemble process, then the co-assembles were used to photocatalytic degradation MO under visible light. The presence of Au NPs enhanced efficiency and nanocomposites revealed unique density-dependent catalytic properties with the increase of Au NPs coverage.