Subnanoclusters have emerged as an exciting platform in heterogeneous catalysis due to their high metal utilization and superior performance. However, understanding the dynamic reconstruction of the active sites of these isomers under experimental conditions is crucial. Herein, we represent a multiscale investigation to decode the solvent-dependent fluxionality of Pt₇ and Pt₈ clusters on graphene support in the gas and solvent phases via an implicit solvation model. We show that under electrochemical reactions, high fluxionality associated with the metastable clusters demands a statistical ensemble-based representation to understand their activity trend, in addition to stable global minima (GM). During oxygen reduction reaction (ORR) mechanistic investigation, distinct adsorption behavior, development of the scaling relationship, and reduced overpotential values represent an enhanced ORR activity at the subnano regime, compared to bulk and nanoclusters. Additionally, we observe that the significant charge transfers, the interactions between clusters and support, and the presence of an aqueous environment facilitate the increased contribution from metastable isomers within the low-energy metastable ensembles (LEMEs) toward overall ORR activity. At last, through ab initio thermodynamic analysis, we represent the stable oxidized phase and activity of the Pt clusters under the ORR conditions. Our approach emphasizes the significance of investigating support and solvent-dependent metastability-triggered reactivity to address the complexities of electrified interfaces in catalytic simulations.

中文翻译：

---

研究石墨烯上 Pt7,8 簇的亚稳态触发反应性：揭示气相和隐式溶剂相中 ORR 的统计系综表示

由于其高金属利用率和卓越的性能，亚纳米团簇已成为多相催化领域令人兴奋的平台。然而，了解这些异构体活性位点在实验条件下的动态重建至关重要。在此，我们进行了一项多尺度研究，通过隐式溶剂化模型解码石墨烯支撑上的 Pt ₇和 Pt ₈簇在气相和溶剂相中的溶剂依赖性流动性。我们表明，在电化学反应下，除了稳定的全局最小值（GM）之外，与亚稳态团簇相关的高流动性还需要基于统计系综的表示来了解其活动趋势。在氧还原反应 (ORR) 机理研究过程中，与本体和纳米团簇相比，不同的吸附行为、缩放关系的发展以及降低的过电势值代表了亚纳米区域的 ORR 活性增强。此外，我们观察到显着的电荷转移、簇与载体之间的相互作用以及水环境的存在促进了低能亚稳系综（LEME）内的亚稳异构体对整体 ORR 活性的贡献增加。最后，通过从头算热力学分析，我们表征了ORR条件下Pt团簇的稳定氧化相和活性。我们的方法强调了研究支持和溶剂依赖性亚稳态触发反应性的重要性，以解决催化模拟中带电界面的复杂性。