Coordination Inversion of the Tetrahedrally Coordinated Ru4f Surface Complex on RuO2(100) and Its Decisive Role in the Anodic Corrosion Process,ACS Catalysis

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Coordination Inversion of the Tetrahedrally Coordinated Ru4f Surface Complex on RuO2(100) and Its Decisive Role in the Anodic Corrosion Process
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-02-23 , DOI: 10.1021/acscatal.2c06260
Franziska Hess ₁ , Herbert Over _{2,

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Affiliation

The c(2 × 2) reconstruction of RuO₂(100) leads to unusual and flexible surface functionality in the form of a tetrahedrally coordinated Ru_4f surface complex with distinct chemical properties that are important for the anodic activity and stability in water electrolysis. We employ first-principles methods based on density functional theory calculations to elucidate the hybridization of this Ru_4f surface species and its rich coordination chemistry. Under oxygen evolution reaction (OER) conditions, the consecutive breaking of structural Ru_4f–O back bonds is shown to proceed via the back side attack of Ru_4f (akin to the Walden inversion) by dissociative water adsorption and the release of two proton/electron pairs. This inversion step of the coordination environment of a surface transition metal cation is considered to be the key step in the anodic dissolution process. Oxygen evolution over Ru_4f on RuO₂(100)–c(2 × 2) competes with its dissolution. From ab initio thermodynamics, the inherent OER activity over Ru_4f is shown to be lower than that of Ru surface sites on the unreconstructed RuO₂(100), while the dissolution propensity of the Ru_4f surface complex is higher. This finding calls into question the frequently stated hypothesis that higher activity is correlated with a lower stability of the active center.

中文翻译：

四面体配位的 Ru4f 表面络合物在 RuO2(100) 上的配位反转及其在阳极腐蚀过程中的决定性作用

RuO ₂ (100) 的c (2 × 2) 重构以四面体配位的 Ru _4f表面复合物的形式产生异常灵活的表面功能，具有独特的化学性质，这对水电解中的阳极活性和稳定性很重要。我们采用基于密度泛函理论计算的第一性原理方法来阐明这种 Ru _4f表面物种的杂化及其丰富的配位化学。_{在析氧反应 (OER) 条件下，结构 Ru 4f} –O 背键的连续断裂显示是通过 Ru _4f的背面攻击进行的（类似于 Walden 反转）通过离解水吸附和两个质子/电子对的释放。这种表面过渡金属阳离子配位环境的反转步骤被认为是阳极溶解过程中的关键步骤。RuO ₂ (100)– c (2 × 2) 上的 Ru _4f上的氧释放与其溶解竞争。_{从 ab initio 热力学来看，Ru 4f}的固有 OER 活性低于未重构 RuO ₂ (100) 上的 Ru 表面位点，而 Ru _{4f的溶解倾向}表面络合物较高。这一发现对经常提出的假设提出了质疑，即较高的活动与活动中心的较低稳定性相关。

更新日期：2023-02-23

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