Nørskov and collaborators proposed a simple kinetic model to explain the volcano relation for the hydrogen evolution reaction on transition metal surfaces such that j₀ = k₀f(ΔG_H) where j₀ is the exchange current density, f(ΔG_H) is a function of the hydrogen adsorption free energy ΔG_H as computed from density functional theory, and k₀ is a universal rate constant. Herein, focusing on the hydrogen evolution reaction in acidic medium, we revisit the original experimental data and find that the fidelity of this kinetic model can be significantly improved by invoking metal-dependence on k₀ such that the logarithm of k₀ linearly depends on the absolute value of ΔG_H. We further confirm this relationship using additional experimental data points obtained from a critical review of the available literature. Our analyses show that the new model decreases the discrepancy between calculated and experimental exchange current density values by up to four orders of magnitude. Furthermore, we show the model can be further improved using machine learning and statistical inference methods that integrate additional material properties.

中文翻译：

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重新审视析氢交换电流的趋势

Nørskov 和合作者提出了一个简单的动力学模型来解释过渡金属表面析氢反应的火山关系，使得j ₀ = k ₀ f (Δ G _H ) 其中j ₀是交换电流密度f (Δ G _H )是根据密度泛函理论计算的氢吸附自由能 Δ G _{H 的}函数，并且k ₀是一个普遍的速率常数。在此，着眼于在酸性介质中的氢生成反应，我们重新审视原始实验数据和发现，这种动力学模型的保真度可以显著通过调用金属依赖性改进ķ ₀，使得对数ķ ₀线性地依赖于Δ G _{H 的}绝对值. 我们使用从现有文献的批判性审查中获得的额外实验数据点进一步证实了这种关系。我们的分析表明，新模型将计算和实验交换电流密度值之间的差异减少了多达四个数量级。此外，我们展示了可以使用机器学习和统计推断方法进一步改进模型，这些方法集成了额外的材料属性。