Carbon Nanotube-Templated Synthesis of Covalent Porphyrin Network for Oxygen Reduction Reaction
Carbon Nanotube-Templated Synthesis of Covalent Porphyrin Network for Oxygen Reduction Reaction
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DOI：
10.1021/ja500984k
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发表时间：
2014-04-30
影响因子：
15
通讯作者：
Campidelli, Stephane
中科院分区：
文献类型：
--
作者：
Hijazi, Ismail;Bourgeteau, Tiphaine;Campidelli, Stephane
开发创新的碳纳米管功能化技术，既能保持其优异的品质，又能丰富其性能，这是碳纳米管集成应用的核心问题。在这项工作中，我们描述了在MWNT表面形成的卟啉共价网络。该方法是基于钴（II）中四乙基卟啉在纳米管侧壁上的吸附，然后通过hay偶联使三键二聚化；在反应过程中，纳米管作为聚合物层形成的模板。由于卟啉和纳米管之间的多重pi堆叠相互作用的协同效应以及卟啉之间的共价连接，该材料显示出更高的稳定性。对纳米管杂化物进行了全面表征，并通过一系列电化学测试对其作为氧还原反应（ORR）的负载催化剂进行了测试。酸性条件。与单体卟啉被简单物理吸附的类似体系相比，MWNT-CoP杂化物显示出更高的ORR活性，其交换电子数接近4，对应于氧完全还原成水。
The development of innovative techniques for the functionalization of carbon nanotubes that preserve their exceptional quality, while robustly enriching their properties, is a central issue for their integration in applications. In this work, we describe the formation of a covalent network of porphyrins around MWNT surfaces. The approach is based on the adsorption of cobalt(II) meso-tetraethynylporphyrins on the nanotube sidewalls followed by the dimerization of the triple bonds via Hay-coupling; during the reaction, the nanotube acts as a template for the formation of the polymeric layer. The material shows an increased stability resulting from the cooperative effect of the multiple pi-stacking interactions between the porphyrins and the nanotube and by the covalent links between the porphyrins. The nanotube hybrids were fully characterized and tested as the supported catalyst for the oxygen reduction reaction (ORR) in a series of electrochemical measurements under. acidic conditions. Compared to similar systems in which monomeric porphyrins are simply physisorbed, MWNT-CoP hybrids showed a higher ORR activity associated with a number of exchanged electrons close to four, corresponding to the complete reduction of oxygen into water.