Unlocking the Potential of Isolated Pt Atoms for NH 3 –SCO Reactions via Modulating Orbital Coupling in Heteroatom Ensembles

作者：Yanfei Liu, Zhang Liu, Yi Yu, Chun Du, Jie Xu, Yaohui Dun, Chengxiong Wang, Yunkun Zhao, Aimin Zhang, Fudong Liu, Wei Li, Rong Chen, Bin Shan · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c01032 · 被引用次数：10 · 研究领域：Asymmetric Hydrogenation and Catalysis、Ammonia Synthesis and Nitrogen Reduction、Nanomaterials for catalytic reactions

Isolated atom catalysts face challenges in structure-sensitive reactions due to their oxidic electronic states and the lack of ensemble sites. A strategy employing the coupling between the coordination environment and adsorbate species is developed to overcome these limitations by constructing PtCu heteroatom ensembles, which unleashes the latent power of isolated Pt atoms for NH 3 –SCO reactions. Through the integrated exploration of theoretical calculations and experimental studies, we elucidate the pivotal role of structural sensitivity and isolated Pt coordination environments in shaping the electronic structure of Pt and its interaction with adsorbates. Our work reveals the Cu–Pt 1 –Cu atomic site as a breakthrough configuration, displaying unprecedented catalytic activity and selectivity in NH 3 –SCO reactions, far surpassing traditional Pt-based catalysts. Remarkably, the dispersed Cu–Pt 1 –Cu heteroatom ensemble achieves a turnover frequency of 0.29 s –1 at 150 °C, being the highest among Pt-based catalysts, and outperforming representative Pt 1 SACs by an impressive 6 orders of magnitude, while its N 2 selectivity remains above 89.7%. This heightened performance is attributed to its distinctive electronic properties, characterized by free-atom-like metallic Pt electronic orbitals embedded within a bulk like Pt 1 –Cu n ensemble structure.