Unlocking the Potential of Isolated Pt Atoms for NH3–SCO Reactions via Modulating Orbital Coupling in Heteroatom Ensembles

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 NH3–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–Pt1–Cu atomic site as a breakthrough configuration, displaying unprecedented catalytic activity and selectivity in NH3–SCO reactions, far surpassing traditional Pt-based catalysts. Remarkably, the dispersed Cu–Pt1–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 Pt1 SACs by an impressive 6 orders of magnitude, while its N2 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 Pt1–Cun ensemble structure.