The electric absorption spectra of axial coordination reactions of tailed phenylalanine tetraphenylporphyrinato cobalt(Ⅱ) Co[Phe-TPP]with imidazole(Im),2 Methyl imidazole(2 MeIm) and N Methylimidazole(N MeIm) have be...The electric absorption spectra of axial coordination reactions of tailed phenylalanine tetraphenylporphyrinato cobalt(Ⅱ) Co[Phe-TPP]with imidazole(Im),2 Methyl imidazole(2 MeIm) and N Methylimidazole(N MeIm) have been studied.The standard equilibrium constant K and stoichiometric number n of reaction were measured by visible spectroscopy.The changes of standard molar enthalpy Δ rH m and standard molar entropy Δ rS m of the reaction were obtained from the plots of lnK υs 1/T.展开更多
Simple cobalt tetraphenylporphyrins was synthesized and used to catalyze cyclohexene oxidation into cyclohexenone with air in the absence of additives and solvents.The cobalt metalloporphyrin was found to be very effe...Simple cobalt tetraphenylporphyrins was synthesized and used to catalyze cyclohexene oxidation into cyclohexenone with air in the absence of additives and solvents.The cobalt metalloporphyrin was found to be very effective catalysts for the synthesis of cyclohexenone from cyclohexene.The research results showed that the temperature, air velocity,catalyst concentration and pressure influenced the yield and conversion of cyclohexene oxidation with air.For cyclohexene oxidation catalyzed by simple cobalt tetraphenylporphyrin, the conversion of cyclohexene was up to 21%, the yield of cyclohexenone reached 75%, under the optimum conditions of 0.4 MPa, 80 ℃ and 2.3×10 -5 mol·L -1 cobalt tetraphenylporphyrin.展开更多
This paper reports the thermodynamics of reversible oxygen binding to a dicobalt di(meso-tetraphenylporphyrin) linked by a diamido- aliphatic chain in N, Ndimethylformamide solution. Thermodynamic values(standard stat...This paper reports the thermodynamics of reversible oxygen binding to a dicobalt di(meso-tetraphenylporphyrin) linked by a diamido- aliphatic chain in N, Ndimethylformamide solution. Thermodynamic values(standard state 101325 Pa O2): △G (298K)=-3.1kJ mol-1, △H (298K)=-37.1kJ·mol-1, △S (298K)=-114 J.mol-1K-1,Co:O2=1:1. The ESR parameters of the dioxygen complex in DMF at 133K are as follows: g=2.000, g=2.046, A= 15G, A =22G, The pressure of dioxygen necessary for half-oxygenation of the system (P1/2 =42.7kPa at 288K) is comparable with that for cobalt substituted human hemoglobin at T state.展开更多
金属卟啉具有高的共轭结构和化学稳定性,在酸性和碱性介质中均表现良好的ORR电催化活性。以周边不含有易聚合官能团的四苯基钴卟啉(Co TPP)为单体,采用循环伏安电化学聚合的方法制备四苯基钴卟啉聚合物(p Co TPP)薄膜。由于生成的聚合...金属卟啉具有高的共轭结构和化学稳定性,在酸性和碱性介质中均表现良好的ORR电催化活性。以周边不含有易聚合官能团的四苯基钴卟啉(Co TPP)为单体,采用循环伏安电化学聚合的方法制备四苯基钴卟啉聚合物(p Co TPP)薄膜。由于生成的聚合物具有更高的共轭结构,p Co TPP薄膜的紫外光谱图中Soret带和Q带均发生红移,且吸收峰变宽。结果表明,p Co TPP在碱性介质中对氧分子具有良好的电催化活性,为金属卟啉氧还原反应(ORR)催化剂的研究提供新的方向,有望成为燃料电池非贵金属氧还原催化剂材料。展开更多
文摘The electric absorption spectra of axial coordination reactions of tailed phenylalanine tetraphenylporphyrinato cobalt(Ⅱ) Co[Phe-TPP]with imidazole(Im),2 Methyl imidazole(2 MeIm) and N Methylimidazole(N MeIm) have been studied.The standard equilibrium constant K and stoichiometric number n of reaction were measured by visible spectroscopy.The changes of standard molar enthalpy Δ rH m and standard molar entropy Δ rS m of the reaction were obtained from the plots of lnK υs 1/T.
文摘Simple cobalt tetraphenylporphyrins was synthesized and used to catalyze cyclohexene oxidation into cyclohexenone with air in the absence of additives and solvents.The cobalt metalloporphyrin was found to be very effective catalysts for the synthesis of cyclohexenone from cyclohexene.The research results showed that the temperature, air velocity,catalyst concentration and pressure influenced the yield and conversion of cyclohexene oxidation with air.For cyclohexene oxidation catalyzed by simple cobalt tetraphenylporphyrin, the conversion of cyclohexene was up to 21%, the yield of cyclohexenone reached 75%, under the optimum conditions of 0.4 MPa, 80 ℃ and 2.3×10 -5 mol·L -1 cobalt tetraphenylporphyrin.
文摘This paper reports the thermodynamics of reversible oxygen binding to a dicobalt di(meso-tetraphenylporphyrin) linked by a diamido- aliphatic chain in N, Ndimethylformamide solution. Thermodynamic values(standard state 101325 Pa O2): △G (298K)=-3.1kJ mol-1, △H (298K)=-37.1kJ·mol-1, △S (298K)=-114 J.mol-1K-1,Co:O2=1:1. The ESR parameters of the dioxygen complex in DMF at 133K are as follows: g=2.000, g=2.046, A= 15G, A =22G, The pressure of dioxygen necessary for half-oxygenation of the system (P1/2 =42.7kPa at 288K) is comparable with that for cobalt substituted human hemoglobin at T state.
文摘金属卟啉具有高的共轭结构和化学稳定性,在酸性和碱性介质中均表现良好的ORR电催化活性。以周边不含有易聚合官能团的四苯基钴卟啉(Co TPP)为单体,采用循环伏安电化学聚合的方法制备四苯基钴卟啉聚合物(p Co TPP)薄膜。由于生成的聚合物具有更高的共轭结构,p Co TPP薄膜的紫外光谱图中Soret带和Q带均发生红移,且吸收峰变宽。结果表明,p Co TPP在碱性介质中对氧分子具有良好的电催化活性,为金属卟啉氧还原反应(ORR)催化剂的研究提供新的方向,有望成为燃料电池非贵金属氧还原催化剂材料。
