Revealing the importance of kinetics in N-coordinated dual-metal sites catalyzed oxygen reduction reaction
Revealing the importance of kinetics in N-coordinated dual-metal sites catalyzed oxygen reduction reaction
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DOI：
10.1016/j.jcat.2021.02.016
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发表时间：
2021-03
影响因子：
7.3
通讯作者：
Feiteng Wang;Wenbo Xie;Lijun Yang;D. Xie;Sen Lin
中科院分区：
文献类型：
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作者：
Feiteng Wang;Wenbo Xie;Lijun Yang;D. Xie;Sen Lin
本文从第一性原理出发，通过引入两个重要因素(零电荷势和O-O键断裂的势相关动力学)，系统地研究了双金属氮碳催化剂上的氧还原反应过程。我们的结果表明，双金属中心的高活性可以归因于在ORR过程中引入第二个金属中心可以促进关键的OH*中间体上的O-O键的断裂，同时缓解了*OH的去除问题。重要的是，我们定义了一个称为“反键中心”的描述符，它简化了动力学的评估。基于本工作所采用的先进方法，我们证明了几种DM-N-C电催化剂，包括FeFeN6、FeCoN6和CoZnN6，具有与以往实验一致的高的ORR活性，并预测MnCoN6对酸性ORR具有更高的稳定性和活性。本研究论证了在酸性电解液中ORR具有双金属中心的优势，并强调了动力学在ORR电催化剂理论研究中的重要意义。
In this work, the oxygen reduction reaction (ORR) process on dual-metal-nitrogen-carbon (DM-N-C) catalysts by including two important factors (potential of zero charge and potential-dependent kinetics of O-O bond cleavage) from first-principle calculations is systematically investigated. Our results reveal that the origin for the high activity of dual-metal sites can be attributed to the fact that introducing a second metal site can facilitate the O-O bond cleavage in the key OOH* intermediate during ORR and meanwhile mitigate the *OH removal issue. Importantly, we define a descriptor called “antibonding center” that simplifies the evaluation of the kinetics. Based on the advanced approach used in this work, we demonstrate that several DM-N-C electrocatalysts including FeFeN6, FeCoN6, and CoZnN6have high ORR activity consistent with previous experiments, and also predict MnCoN6can be more highly stable and active for acidic ORR. This study demonstrates the advantage of the dual metal sites for the ORR in acidic electrolyte and highlights the significance of kinetics in the theoretical study of ORR electrocatalysts.