What is the Real Origin of the Activity of Fe–N–C Electrocatalysts in the O2 Reduction Reaction? Critical Roles of Coordinating Pyrrolic N and Axially Adsorbing Species,Journal of the American Chemical Society

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What is the Real Origin of the Activity of Fe–N–C Electrocatalysts in the O2 Reduction Reaction? Critical Roles of Coordinating Pyrrolic N and Axially Adsorbing Species
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-09-22 , DOI: 10.1021/jacs.2c08743
Xu Hu ₁ , Suya Chen ₁ , Letian Chen ₁ , Yun Tian ₂ , Sai Yao ₁ , Zhengyu Lu ₁ , Xu Zhang ₂ , Zhen Zhou _{1,

2}

Affiliation

Fe–N–C electrocatalysts have emerged as promising substitutes for Pt-based catalysts for the oxygen reduction reaction (ORR). However, their real catalytic active site is still under debate. The underlying roles of different types of coordinating N including pyridinic and pyrrolic N in catalytic performance require thorough clarification. In addition, how to understand the pH-dependent activity of Fe–N–C catalysts is another urgent issue. Herein, we comprehensively studied 13 different N-coordinated FeN_xC configurations and their corresponding ORR activity through simulations which mimic the realistic electrocatalytic environment on the basis of constant-potential implicit solvent models. We demonstrate that coordinating pyrrolic N contributes to a higher activity than pyridinic N, and pyrrolic FeN₄C exhibits the highest activity in acidic media. Meanwhile, the in situ active site transformation to *O-FeN₄C and *OH-FeN₄C clarifies the origin of the higher activity of Fe–N–C in alkaline media. These findings can provide indispensable guidelines for rational design of better durable Fe–N–C catalysts.

中文翻译：

Fe-N-C 电催化剂在 O2 还原反应中活性的真正来源是什么？协调吡咯 N 和轴向吸附物质的关键作用

Fe-N-C 电催化剂已成为氧还原反应 (ORR) 铂基催化剂的有希望的替代品。然而，它们真正的催化活性位点仍在争论中。不同类型的配位氮（包括吡啶和吡咯氮）在催化性能中的潜在作用需要彻底阐明。此外，如何理解 Fe-N-C 催化剂的 pH 依赖性活性是另一个紧迫的问题。在此，我们通过模拟基于恒电位隐式溶剂模型的真实电催化环境，全面研究了 13 种不同的 N 配位 FeN _{x C 构型及其相应的 ORR 活性。}我们证明了配位吡咯 N 比吡啶 N 和吡咯 FeN 具有更高的活性₄ C 在酸性介质中表现出最高的活性。同时，活性位点向*O-FeN ₄ C和*OH-FeN _{4 C}的原位转变阐明了Fe-N-C在碱性介质中具有较高活性的原因。这些发现可以为合理设计更耐用的 Fe-N-C 催化剂提供不可或缺的指导。

更新日期：2022-09-22

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