This work presents a new theoretical framework to construct volcano relations (VRs) that are capable of predicting and understanding the activity of top electrocatalysts. We propose a thermodynamic form of the energetic span (δE) as a rate-determining term for electrocatalytic reactions, which allows the essential factors such as the coverage of the stable intermediates and the energetics of the most demanding steps to be included in the rate equations and therefore overcomes the weakness of the current electrocatalytic VRs derived from kinetic models using the maximum standard free energy (ΔG_max^°) of elementary reaction steps as rate-determining terms. The ΔG_max^°-based VRs are shown to be applicable only at large overpotentials, where the intermediates involved in δE and ΔG_max^° converge. At small overpotentials, where the excellent catalysts function, the ΔG_max^°-based VRs may give improper predictions by missing the effects of the surface phases of stable adsorbates and their evolution with the potential. As well as revealing new features of electrocatalytic VRs and reasonably explaining some recent experimental results on efficient electrocatalysts for the hydrogen and oxygen electrode reactions, the δE-based rate models provide rich information about the catalytic mechanism and kinetics, e.g., the evolution of surface phases of stable intermediates, rate-determining transition states, and Tafel slopes.

中文翻译：

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高能跨度作为电催化火山的速率决定项

这项工作提出了一个新的理论框架，以构建能够预测和理解顶级电催化剂活性的火山关系（VR）。我们提出了高能跨度的热力学形式（δ ë）作为电催化反应的速率决定术语，它允许诸如稳定的中间体的覆盖范围和最苛刻的步骤的能量学的要素将被包括在所述速率方程并因此克服了从动力学模型得出的当前电催化VR的弱点，该动力学模型使用基本反应步骤的最大标准自由能（ΔG _max ^°）作为速率确定项。该Δ ģ_最大^°系的VR只示出了在大的超电势，为可应用于其中参与δ中间体È和Δ ģ_最大^°会聚。在小的超电势下，在出色的催化剂起作用的情况下，基于ΔG _max ^°的VR可能会错过稳定的吸附物表面相的影响及其随电势的演化而给出不正确的预测。以及露出电VR的新功能，并合理地解释为氢气和氧气的电极反应最近高效电催化剂的一些实验结果中，该δ È基于速率的模型提供了有关催化机理和动力学的丰富信息，例如，稳定中间体的表面相的演变，速率确定的过渡态和塔菲尔斜率。