Identification of Active Sites of Pure and Nitrogen-Doped Carbon Materials for Oxygen Reduction Reaction Using Constant-Potential Calculations,The Journal of Physical Chemistry C

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Identification of Active Sites of Pure and Nitrogen-Doped Carbon Materials for Oxygen Reduction Reaction Using Constant-Potential Calculations
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-05-11 , DOI: 10.1021/acs.jpcc.0c03951
Zhiyao Duan ₁ , Graeme Henkelman ₁

Affiliation

Nitrogen-doped carbon materials are promising metal-free catalysts for the electrochemical oxygen reduction reaction (ORR). A better theoretical understanding on the nature of the active site(s) would help further optimization of their ORR activity. Although quantum mechanical calculations have been widely employed to elucidate the active sites over various catalysts, these calculations are typically done assuming constant-charge conditions rather than the experimentally relevant constant-potential conditions. In this study, we employ the double-reference method to simulate the energetics of the ORR over pure and N-doped carbon materials under constant-potential conditions. We demonstrate that constant-potential calculations enable more accurate theoretical predictions, comparing well with existing experiments. Our key findings are (1) the zigzag edge of pure graphite is highly active for ORR, (2) the pyridinic N-doped armchair edge is highly active for ORR in alkaline media but not in acid, and (3) graphitic N can donate electrons to pyridinic N to enhance the ORR activity. These fundamental insights provide guidelines for the design of better carbon-based ORR catalysts.

中文翻译：

使用恒电位计算确定用于还原氧的纯氮掺杂碳材料的活性位

氮掺杂碳材料是用于电化学氧还原反应（ORR）的有前途的无金属催化剂。对活性部位性质的更好的理论理解将有助于进一步优化其ORR活性。尽管量子力学计算已被广泛用于阐明各种催化剂上的活性位，但是这些计算通常是在假设恒定电荷条件而不是与实验相关的恒定电势条件下进行的。在这项研究中，我们采用双参考方法来模拟恒电位条件下纯氮掺杂碳材料上ORR的能量。我们证明，与现有实验相比，恒电位计算可以实现更准确的理论预测。我们的主要发现是（1）纯石墨的锯齿形边缘对ORR具有高活性，（2）吡啶氮掺杂的扶手椅形边缘在碱性介质中对ORR具有高活性，而在酸中则无活性，以及（3）石墨氮可以提供电子转化为吡啶二氮，以增强ORR活性。这些基本见解为设计更好的碳基ORR催化剂提供了指导。

更新日期：2020-05-11

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