随着全球能源需求的迅猛增长,氢能作为一种清洁、高效的能源,其重要性日益凸显。电解水作为制备氢气的理想方法,其效率的提升关键在于优化两个核心反应:析氧反应(OER)和析氢反应(HER)。然而,OER由于其复杂的四电子转移过程和缓慢的动力...随着全球能源需求的迅猛增长,氢能作为一种清洁、高效的能源,其重要性日益凸显。电解水作为制备氢气的理想方法,其效率的提升关键在于优化两个核心反应:析氧反应(OER)和析氢反应(HER)。然而,OER由于其复杂的四电子转移过程和缓慢的动力学特性,成为了限制电解水技术效率提升的关键瓶颈。为了深入研究OER的反应机制,本文借助沸石咪唑酯骨架(ZIF)材料的独特优势,将钴卟啉负载在ZIF材料上,制备了一系列以ZIF材料为基底的OER催化剂。电化学测试表明,钴卟啉@Ni/Co-ZIF复合材料在碱性条件下具有较好的析氧性能,在10 mA cm−2电流密度下的过电位为345 mV,Tafel斜率为95 mV dec−1,且拥有良好的稳定性。With the rapid growth of global energy demand, hydrogen energy as a clean and efficient energy carrier, its importance has become increasingly prominent. Water splitting is an ideal method for hydrogen production, and the key to improve its efficiency is to optimize two core reactions: Oxygen evolution (OER) and hydrogen evolution (HER). However, due to its complex four-electron transfer process and slow kinetic characteristics, OER has become a key bottleneck limiting the efficiency of electrolytic water technology. In order to further study the reaction mechanism of OER, a series of OER catalysts based on zeolite imidazolate framework (ZIF) were prepared by loading cobalt porphyrin on ZIF material with the advantage of ZIF. Electrochemical tests show that cobalt porphyrin@Ni/Co-ZIF material has good oxygen evolution performance with overpotential of 345 mV at 10mA cm−2 current density and Tafel slope of 95 mV dec−1, and good stability under alkaline conditions.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
文摘随着全球能源需求的迅猛增长,氢能作为一种清洁、高效的能源,其重要性日益凸显。电解水作为制备氢气的理想方法,其效率的提升关键在于优化两个核心反应:析氧反应(OER)和析氢反应(HER)。然而,OER由于其复杂的四电子转移过程和缓慢的动力学特性,成为了限制电解水技术效率提升的关键瓶颈。为了深入研究OER的反应机制,本文借助沸石咪唑酯骨架(ZIF)材料的独特优势,将钴卟啉负载在ZIF材料上,制备了一系列以ZIF材料为基底的OER催化剂。电化学测试表明,钴卟啉@Ni/Co-ZIF复合材料在碱性条件下具有较好的析氧性能,在10 mA cm−2电流密度下的过电位为345 mV,Tafel斜率为95 mV dec−1,且拥有良好的稳定性。With the rapid growth of global energy demand, hydrogen energy as a clean and efficient energy carrier, its importance has become increasingly prominent. Water splitting is an ideal method for hydrogen production, and the key to improve its efficiency is to optimize two core reactions: Oxygen evolution (OER) and hydrogen evolution (HER). However, due to its complex four-electron transfer process and slow kinetic characteristics, OER has become a key bottleneck limiting the efficiency of electrolytic water technology. In order to further study the reaction mechanism of OER, a series of OER catalysts based on zeolite imidazolate framework (ZIF) were prepared by loading cobalt porphyrin on ZIF material with the advantage of ZIF. Electrochemical tests show that cobalt porphyrin@Ni/Co-ZIF material has good oxygen evolution performance with overpotential of 345 mV at 10mA cm−2 current density and Tafel slope of 95 mV dec−1, and good stability under alkaline conditions.
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。
