A Universal Descriptor for the Screening of Electrode Materials for Multiple-Electron Processes: Beyond the Thermodynamic Overpotential
A Universal Descriptor for the Screening of Electrode Materials for Multiple-Electron Processes: Beyond the Thermodynamic Overpotential
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DOI：
10.1021/acscatal.0c03865
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发表时间：
2020-11-06
期刊：
影响因子：
12.9
通讯作者：
Exner, Kai S.
中科院分区：
文献类型：
--
作者：
Exner, Kai S.
在实现可持续能源经济的道路上，需要开发不含稀有贵金属的电极材料。以低计算成本操作，材料筛选是通过将材料分类为活性和非活性来评估潜在电极组合物的性能的有力工具。最常见的是，线性标度关系分析的火山图，其中的热力学超电位，eta（TD），作为活动描述符的建设。即使该描述符识别了大多数活性电极材料，据报道，η（TD）缺乏根据其活性对催化剂的彻底分类。该失效主要与η（TD）由单个自由能变化（热力学）定义的事实有关，而在分析中没有考虑所施加的过电位和动力学。基于对自由能图和速率决定反应步骤的讨论，本观点引入了多电子过程的替代活性描述符G（max）（eta），从而在评估中包括了应用的过电位和动力学效应。以析氧反应为例，讨论了G（max）（eta）在电极材料筛选和优化中的应用，与传统的eta（TD）方案相比，提供了不同的视角。
On the way toward a sustainable energy economy, electrode materials that do not contain scarce noble metals need to be developed. Operating at low computational costs, material screening is a powerful tool to assess the performance of potential electrode compositions by categorizing materials into active and inactive. Most commonly, linear scaling relationships are analyzed by the construction of a volcano plot, in which the thermodynamic overpotential, eta(TD), serves as activity descriptor. Even if this descriptor identifies the majority of active electrode materials, it has been reported that eta(TD) lacks thorough sorting of catalysts according to their activity. This failure is mainly related to the fact that eta(TD) is defined by a single free-energy change (thermodynamics), whereas the applied overpotential and kinetics are not factored in the analysis. Based on the discussion of free-energy diagrams and the rate-determining reaction step, this Viewpoint introduces an alternate activity descriptor, G(max)(eta), for multiple-electron processes, thereby including the applied overpotential and kinetic effects in the evaluation. On the example of the oxygen evolution reaction, the application of G(max)(eta) for the screening and optimization of electrode materials is discussed, providing a different perspective compared with the conventional scheme of eta(TD).