We present a first-principles-based formalism to provide a quantitative measure of the thermodynamic instability and propensity for electrochemical stabilization, passivation, or corrosion of metastable materials in aqueous media. We demonstrate that this formalism can assess the relative Gibbs free energy of candidate materials in aqueous media as well as their decomposition products, combining solid and aqueous phases, as a function of pH and potential. On the basis of benchmarking against 20 stable as well as metastable materials reported in the literature and also our experimental characterization of metastable triclinic-FeVO₄, we present quantitative estimates for the relative Gibbs free energy and corresponding aqueous regimes where these materials are most likely to be stable, form inert passivating films, or steadily corrode to aqueous species. Furthermore, we show that the structure and composition of the passivating films formed on triclinic-FeVO₄ are also in excellent agreement with the Point Defect Model, as proposed by the corrosion community. An open-source web application based on the formalism is made available at https://materialsproject.org.

中文翻译：

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亚稳材料的电化学稳定性

我们提出了一种基于第一原理的形式主义，以定量地测量热稳定性和钝化材料在水性介质中的电化学稳定性，钝化或腐蚀的热力学不稳定性和倾向。我们证明了这种形式主义可以评估候选物质在水性介质及其分解产物中的相对吉布斯自由能，结合固相和水相，作为pH和电位的函数。在以文献报道的20种稳定和亚稳材料为基准以及我们对亚稳三斜晶FeVO _4的实验表征的基础上，我们提供了相对吉布斯自由能的定量估计，以及相应的水溶液形式，在这些形式下，这些材料最可能稳定，形成惰性钝化膜或稳定腐蚀水性物质。此外，我们表明，在三斜晶FeVO ₄上形成的钝化膜的结构和组成也与腐蚀社区提出的Point Defect Model十分吻合。可从https://materialsproject.org获得基于形式主义的开源Web应用程序。