Metal-nitrogen-carbon catalysts loaded on fluorinated carbon nanotubes for efficient oxygen reduction reaction
Metal-nitrogen-carbon catalysts loaded on fluorinated carbon nanotubes for efficient oxygen reduction reaction
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DOI：
10.1007/s42114-023-00663-y
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发表时间：
2023-04
影响因子：
20.1
通讯作者：
Zhichuan Zheng;Xuekun Hong;Dajun Wu;Ninglei Sun;Y. Kuang;Debao Zhang;Xiaxi Yao;P. Du;Kai Huang
中科院分区：
文献类型：
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作者：
Zhichuan Zheng;Xuekun Hong;Dajun Wu;Ninglei Sun;Y. Kuang;Debao Zhang;Xiaxi Yao;P. Du;Kai Huang
近年来，在研究的各种非贵金属催化剂中，过渡金属-氮-碳（M–N-C）复合材料有望成为铂族金属（PGM）的替代品。然而，主要挑战来自电催化性能和氧还原反应（ORR）耐久性不足。除了选择合适的中心金属活性位点外，还可以通过调整催化剂的电子结构来增强M-N-C催化剂的电催化活性和稳定性。在这项工作中，通过简单的热解方法将过渡金属酞菁配合物负载到预氟化碳纳米管上合成了M-N-C/F复合材料。热处理后形成的吡咯啉-N（PN）和石墨-N（GN）可以作为电子受体来调节其在M-N4位点上的电荷分布，并且预氟化纳米管的使用还可以更受控地引入与过渡金属良好配位的氟离子，两者都可以调节和修饰M-N-C催化剂的电子结构。所获得的锰酞菁/氟化碳纳米管在800℃下（MnPc/FCNT800）表现出具有竞争力的电催化ORR性能，半波电位（E1/2）为0.9V，在1.0M KOH电解质中经过20小时长期计时电流（CA）测试后仅衰减12.1%，优于商业Pt/C。总体而言，这项工作为此类 M-N-C 复合材料用于可持续能源应用的电子结构修改和设计铺平了道路。图形摘要
In recent years, transition metal-nitrogen-carbon (M–N-C) composites are expected to be an alternative to platinum group metal (PGM) among various non-precious metal catalysts investigated. However, the major challenge comes from insufficient electrocatalytic performance and durability for oxygen reduction reaction (ORR). In addition to the selection of suitable central metal active sites, the electrocatalytic activity and stability of the M–N-C catalysts can be enhanced by adjusting the electronic structure of the catalysts. In this work, M–N-C/F composites were synthesized by loading transition metal phthalocyanine complexes onto pre-fluorinated carbon nanotubes through a simple pyrolysis method. Pyrroline-N (PN) and graphite-N (GN) formed after thermal treatment can act as electron acceptors to modulate their charge distribution on the M-N4sites, and the use of pre-fluorinated nanotubes also allows for a more controlled introduction of fluoride ions that are well coordinated to transition metals, both of which can modulate and modify the electronic structure of M–N-C catalysts. The obtained manganese phthalocyanine/fluorinated carbon nanotubes at 800 °C (MnPc/FCNT800) exhibit a competitive electrocatalytic ORR performance with the half-wave potential (E1/2) of 0.9 V and only 12.1% decay after 20-h long-term chronoamperometry (CA) test in 1.0 M KOH electrolyte, outperforming the commercial Pt/C. Overall, this work paves the way of the electronic structure modification and design of such M–N-C composites for sustainable energy applications.Graphical Abstract