The performance of supported metal catalysts, such as nickel nanoparticles decorating yttria-stabilized zirconia (YSZ), depends on their microstructure and the metal–support interface. Here, we have used spin polarized density functional theory (DFT) to evaluate different Ni cluster geometries and determined the electronic structure of the most stable configurations. We have described the interaction of Ni_n (n = 1–10) clusters supported on the cubic ZrO₂(111) and YSZ(111) surfaces, which show a preference for pyramidal shapes rather than flat structures wetting the surface. The interfacial interaction is characterized by charge transfer from the cluster to the surface. We also show how yttrium, present in YSZ, affects the Ni–Ni interaction. Through analysing the difference between the cohesive energy and the clustering energy, we show the preference of Ni–Ni bond formation over Ni-surface interaction; this energy difference decreases with the increase of the Ni_n cluster size. From the evaluation of the Ni atomic hopping rates on YSZ, we have demonstrated that under different temperature conditions, Ni atoms aggregate with other atoms and clusters, which affects the cluster size stability.

中文翻译：

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 ZrO ₂（111）和YSZ（111）表面上支撑的Ni _n（n = 1-10）团簇的稳定性和迁移率：密度泛函理论研究

负载型金属催化剂的性能，例如装饰氧化钇稳定的氧化锆（YSZ）的镍纳米粒子，取决于其微观结构和金属-载体界面。在这里，我们使用自旋极化密度泛函理论（DFT）评估了不同的Ni团簇几何形状，并确定了最稳定构型的电子结构。我们已经描述了立方ZrO ₂上支持的Ni _n（n = 1–10）团簇的相互作用（111）和YSZ（111）表面，它们显示了金字塔形状而不是润湿表面的平坦结构。界面相互作用的特征是电荷从团簇转移到表面。我们还显示了YSZ中存在的钇如何影响Ni-Ni相互作用。通过分析内聚能和聚集能之间的差异，我们显示出Ni-Ni键的形成比Ni-表面的相互作用更具有优势。该能量差随Ni _n团簇尺寸的增加而减小。通过对YSZ上Ni原子跳变率的评估，我们证明了在不同温度条件下，Ni原子会与其他原子和团簇聚集，从而影响团簇尺寸的稳定性。