Preparation And Catalytic Activity Of Natural Polymer Supported Quasi-Porphyrin Metal Complexes

The quasi-porphyrin complexes (such as Metallophthalocyanine and porphyrin) is a class of synthetic compounds, which consists of macrocyclic tetraazaporphyrin structure, and metallophthalocyanine (MPc) has excellent photosensitive capability. So many quasi-porphyrin complexes have been prepared and researched in catalytic fields. The flexibility of the material, Chitosan (CTS), has desirable properties such as low cost, good film-forming ability. In addition, chitosan metal complex exhibits a high catalytic activity and selctivity in many redox reaction. Chitosan is an excellent candidate as a support for catalysis. Supported quasi-porphyrin complexes have received much attention in the field of catalytic reaction, because their use can not only enhance metallic catalysts stability and keep the high-efficiency catalytic activation of metallic catalysts, but they can also be easily separated from the reaction products. Therefore, the new supported catalyst has important significance in catalytic field. In this thesis, a series of polymer supported metallophthalocyanines were prepared and their catalytic activity was also investigated.In chapter 1, quasi-porphyrin complexes'structure and character was introduced, the catalytic activity of supported quasi-porphyrin complexes were also submitted.In chapter 2, the immobilisation of metallophthalocyanine complexes on chitosan membrane (CTS-M-CoPc) was prepared by simple method. They were characterized by FT-IR, UV-Vis, SEM and TG-DTA. Rhodamine B was employed to investigate the photocatalytic activity of CTS-M-CoPc under high pressure Hg lamp illumination. At the present of CTS-M-CoPc, the degradation of RB was carried out, when the initial RB concentration is 1×10^-5 mol/L, the catalyst amount is 0.50 g/L in neutral medium, the color of aqueous RB solutions changed to colorless in short irradiation time, the degration of Rhodamine B was up to 99%. The catalyst showed high catalytic activity and stability for the degradation of Rhodamine B.In chapter 3, the immobilisation of metallophthalocyanine complexes on chitosan microsphere (CTS-MS-CoPc) was prepared by simple method and characterized. Then, cumene was employed to measure its catalytic activity under dioxygen atmosphere. It showed that CTS-MS-CoPc had higher catalytic activity: the oxidation products of cumene were 2-phenyl-2-propyl (PP) and cumene hydroperoxide (CHP). It was found the best reactive condition is as following: reaction temperature was 100℃, the ratio of catalyst to cumene was 1 mg / 2 mL. This oxidation system is also efficient in the oxidation of cyclohexene and aromatic hydrocarbons, which afforded corresponding benzylic oxidation products and epoxides, respectively.In chapter 4, the immobilisation of porphyrin complexes on chitosan microsphere [CTS-MS-TPPS4-M (M=Cu, Zn, Co, Ni)] was prepared by simple method and characterized. Its catalytic activity was also studieded by catalytic oxidation of cumene with molecular oxygen. It showed that CTS-MS-TPPS4Cu had higher catalytic activity.In conclusion, these immobilisation of metallophthalocyanine and porphyrin complexes on chitosan have been prepared and had better catalytic activity. It is a very promising polymer catalyst.