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将结晶CoOOH锚定在氮掺杂碳载体上作为氧还原反应的耐用电催化剂。

Engineering crystalline CoOOH anchored on an N-doped carbon support as a durable electrocatalyst for the oxygen reduction reaction.

作者信息

Zeng Liming, Cui Xiangzhi, Shi Jianlin

机构信息

State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.

出版信息

Dalton Trans. 2018 May 1;47(17):6069-6074. doi: 10.1039/c8dt00826d.

Abstract

Finding highly active, low-cost and stable electro-catalysts for the oxygen reduction reaction is challenging but crucial for several applications such as fuel cells and metal batteries. Herein, we report a novel electro-catalyst of crystalline CoOOH anchored on an N-doped carbon support through a facile method, and we explore its origin of activity via investigating the correlation between the composition of the catalyst and its electrochemical properties. Nitrogen is successfully incorporated into a carbon support, and CoOOH is desirably anchored on a carbon matrix forming Co-N coordination sites in the catalyst, which is revealed to be responsible for the much enhanced oxygen reduction activity compared to the oxygen reduction activities of the electrocatalysts having either single-doped nitrogen or anchored CoOOH species in a carbon support. Furthermore, it is deduced that the active sites for enhanced oxygen reduction can be attributed to Co-Nx, carbon atoms neighboring the doped nitrogen and even the CoOOH species. The optimized catalyst CoOOH@NC-175/300 shows lower onset potential and half-wave potential and much better cyclic stability compared to those of the state-of-the-art Pt/C catalysts. This novel finding provides a new approach for the rational engineering of low-cost, highly active and stable non-precious ORR electrocatalysts for applications in energy conversion and storage.

摘要

寻找用于氧还原反应的高活性、低成本且稳定的电催化剂具有挑战性,但对于燃料电池和金属电池等多种应用而言至关重要。在此,我们报道了一种通过简便方法将结晶态CoOOH锚定在氮掺杂碳载体上的新型电催化剂,并通过研究催化剂组成与其电化学性质之间的相关性来探索其活性来源。氮成功掺入碳载体中,并且CoOOH理想地锚定在碳基质上,在催化剂中形成Co-N配位位点,与在碳载体中具有单掺杂氮或锚定CoOOH物种的电催化剂的氧还原活性相比,该位点被证明是氧还原活性大大增强的原因。此外,据推断,增强氧还原的活性位点可归因于Co-Nx、与掺杂氮相邻的碳原子甚至CoOOH物种。与最先进的Pt/C催化剂相比,优化后的催化剂CoOOH@NC-175/300具有更低的起始电位和半波电位以及更好的循环稳定性。这一新发现为合理设计用于能量转换和存储应用的低成本、高活性和稳定的非贵金属ORR电催化剂提供了一种新方法。

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