Effects of structures of pyrolyzed corrin, corrole and porphyrin on oxygen reduction reaction
Effects of structures of pyrolyzed corrin, corrole and porphyrin on oxygen reduction reaction
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DOI：
10.1016/j.ijhydene.2013.10.082
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发表时间：
2014-01-13
影响因子：
7.2
通讯作者：
Wang, Chen-Hao
中科院分区：
文献类型：
--
作者：
Chang, Sun-Tang;Huang, Hsin-Chih;Wang, Chen-Hao
研究了不同热解钴基大环化合物的结构对氧还原反应（ORR）活性的影响，包括热解钴-corrin化合物（py-Co-Corrin/C）、热解钴-corrole化合物（py-Co-Corrole/C）和热解钴-卟啉化合物（py-Co-Porphyrin/C）。热解后，py-Co-Corrin/C的ORR活性高于py-Co-Corrole/C和py-Co-Porphyrin/C，在0.3 V时，它们的电子转移数分别为3.90、3.87和3.37。根据N- k边近边x射线吸收精细结构分析，只有py-Co-Corrin/C在高温热解时含有Co-N-4螯合物和多芳烃。x射线吸收光谱揭示了钴基大环化合物中中心钴的氧化态由高到低的变化。此外，钴与其相邻元素的原子距离在所有样品中都有所不同。实验结果表明，钴基大环化合物的结构和配位对其ORR活性有很大影响。版权所有(C) 2013，氢能源出版有限责任公司由爱思唯尔有限公司出版版权所有。
The effects of the structures of various pyrolyzed cobalt-based macrocyclic compounds, which are pyrolyzed cobalt-corrin compounds (py-Co-Corrin/C), pyrolyzed cobalt-corrole compounds (py-Co-Corrole/C) and pyrolyzed cobalt-porphyrin compounds (py-Co-Porphyrin/C), on their activities in the oxygen reduction reaction (ORR) are studied. Following the pyrolysis, py-Co-Corrin/C has a higher ORR activity than py-Co-Corrole/C and py-Co-Porphyrin/C, which their electron-transfer numbers are 3.90, 3.87 and 3.37 at 0.3 V, respectively. According to the analysis of near edge X-ray absorption fine structure in N K-edge, only py-Co-Corrin/C has the Co-N-4 chelate and poly-aromatic hydrocarbons when pyrolyzed at high temperature. The X-ray absorption spectra reveal the oxidation states of central cobalt in cobalt-based macrocyclic compounds which are changed from high to low. Also, the atomic distances of cobalt to its neighbors vary among all of the samples. The experimental results suggest that the structure and the coordination of cobalt-based macrocyclic compounds strongly affect their ORR activities. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.