The Study Of Metal Phthalocyanines In The Catalytic Reactions In The Degradation Of Dyes And The Oxidation Of Cyclohexene Iii

Actived carbon fibers(ACFs) and carbon nano fibers(CNFs) were always the object of our research group. Metallophthalocyanine derivatives(MPcs), having analogous structure to the porphyrin derivatives, are highly conjugated macrocyclic compounds which were composed of four isoindole units chaining by imine bridge bond. MPcs have been widely researched as catalysts for the applications in organic synthesis, green chemistry and environmental treatment for its high chemical stablility. Recently, MPcs have received extensively attention in the catalytic oxidation systems using H2O2 as oxidant.In the paper, tertracaboxylic metal phthalocyanines(MTCPcs) and axial coordination phthalocyanines were synthesized at first. For tertracaboxylic metal phthalocyanines, new catalysts(MTCPc Na-AN-CNFs) were obtained through the immobilization technology which TCPcs were immobilized to CNFs by the Billups and amidation reactions respectively. The catalysts were applied to the catalytic degradation of dye wastewater using H2O2 as oxidant. In axial coordination phthalocyanines part, the catalytic oxidation of cyclohexene which was catalyzed by micromolecule catalysts(phthalocyanines) was researched at first. Then, the catalysts(ACFs-Fe Pc X) which phthalocyanines were immobilized to ACFs by physical absorption have been studied for the oxidation of cyclohexene. In order to verify the experiment results and theoretical knowledge, density functional theory(DFT) was employed to indicate the stability and catalytic activity of tertracaboxylic metal phthalocyanines(MTCPcs) and axial coordination phthalocyanines in additional.1. The solid state method of phthalic anhydride-urea route was employed to synthesize MTCPcs(Co TCPc, Fe TCPc and Mn TCPc). New catalysts were obtained through the immobilization technology which TCPcs were immobilized to CNFs by the Billups and amidation reactions respectively. The catalysts shown higher catalytic activity in some ways. 2. Five axial coordination phthalocyanines have been synthesized by the template method. They were Fe Pc NO3, Fe Pc OTf, Fe Pc BF4, Mn Pc NO3 and Mn Pc BF4. 3. In order to further develop “phase transfer in situ catalytic oxidation” for removingother organic pollutants, some dyes have been employed to catalytic degradation by our new catalysts(MTCPc Na-AN-CNFs). Acid orange 7 and Reactive brilliant blue KN-R were selected to research as model dyes. Acid orange 7 can be more effective oxidized than Reactive brilliant blue KN-R in the system of Co TCPc Na-AN-CNFs/H2O2. The introduction of CNFs resulted in a marked enhanced catalytic activity that micromolecule catalysts(phthalocyanines) didn’t have. This system has no negative effect when Na Cl was added; instead, Na Cl is an accelerant for our catalytic degradation system. Therefore, it is an additional advantage for our system to be used practically. 4. In order to verify the experiment results and theoretical knowledge, density functional theory(DFT) was employed to indicate the stability and catalytic activity of tertracaboxylic metal phthalocyanines(TCPcs) and axial coordination phthalocyanines. The results shown below:(a) the order of the total molecular energy level was Mn TCPc > Fe TCPc > Co TCPc. Therefore, the stability of molecular phthalocyanines was Co TCPc > Fe TCPc > Mn TCPc.(b) the order of energy level difference was Mn TCPc > Fe TCPc > Co TCPc, thus catalytic activity of molecular phthalocyanines was Co TCPc > Fe TCPc > Mn TCPc. It was found that the calculation results and the experiment result conformed to each other in the mass. 5. In order to further develop the applied of metal phthalocyanines in catalytic oxidized organic compounds, the system of axial coordination phthalocyanines /H2O2 was established for catalytic oxidized cyclohexene. It was found Fe Pc OTf was the best catalyst, and cyclohexane-1,2-diol was first detected in this system. The best conversion and selective was obtained when the amount of catalyst was 1 mol%, the molar ratio of oxidant and substrate was 1:1, the reaction temperature was 80 ℃, the reaction time was 8 h in the CH3 OH. The conversion of cyclohexene was 97%, meanwhile the selective of cyclohexane-1,2-diol was 51%. 6. Due to excellent adsorption properties and higher chemical stability, ACFs were employed to immobilize axial coordination phthalocyanines by physical absorption. This new catalysts can be recovered for reuse. The results shown that the increase of load amount of axial coordination phthalocyanines to the benefit of the increase ofconversion of cyclohexene. ACFs-Fe Pc OTf had shown the best result. It was found that the rise of reaction temperature and the reaction time extend could enhance the conversion of cyclohexene. The highest conversion of cyclohexene was 42.7%; the selective of 2-cyclohexen-1-one and 2-cyclohexen-1-ol were 44.1% and 55.9% respectively. The introduction of ACFs resulted in a marked enhanced the selectivity of products that micromolecule catalysts(phthalocyanines) didn’t have. 7. In order to verify the experiment results and theoretical knowledge, density functional theory(DFT) was employed to indicate the stability and catalytic activity of axial coordination phthalocyanines. The iron phthalocyanine results shown below:(a) the order of the total molecular energy level was Fe Pc > Fe Pc NO3 > Fe Pc BF4 > Fe Pc Cl > Fe Pc OTf; Therefore, the stability of phthalocyanines was Fe Pc OTf > Fe Pc Cl > Fe Pc BF4 > Fe Pc NO3 > Fe Pc。The substance of redox reaction was charge transfer. The catalytic activity of phthalocyanines according to charge transfer was Fe Pc OTf > Fe Pc > Fe Pc Cl > Fe Pc BF4 > Fe Pc NO3. The results shown that the calculation results and the experiment result conformed to each other in the mass.