Finely TailoringMetal–Support Interactionsvia Transient High-Temperature Pulses

Metal–support interactions (MSI) play a crucial role in enhancing the catalytic activity and stability of metal catalysts by establishing a stable metal-oxide interface. However, precisely controlling MSI at the atomic scale remains a significant challenge, as how to construct an optimal MSI is still not fully understood: Both insufficient and excessive MSI showed inferior catalytic performance. In this study, we propose finely tuning MSI using temporal-precise transient high-temperature pulse heating. Using Pt/CeO₂ as a model system, we systematically investigate how variations in pulse duration and atmosphere influence the reconstruction of the metal–support interface and MSIs. This leads to the formation of two distinct types of MSI: (1) strong MSI (SMSI, Pt@CeO₂) and (2) reactive MSI (RMSI, Pt₅Ce@CeO₂), each with unique compositions, structures, and electrochemical behaviors. Notably, Pt₅Ce@CeO₂ with RMSI exhibits remarkable catalytic performance in the alkaline hydrogen evolution, showing an overpotential of −29 mV and stable operation for over 300 h at −10 mA·cm^–2. Theoretical studies reveal that alloying Pt with Ce to form Pt₅Ce modifies the electronic structure of Pt, shifting the d-band center to optimize the adsorption and dissociation of intermediates, thereby reducing the reaction energy barrier. Moreover, the intimate interaction of Pt₅Ce with CeO₂ further improves the activity and stability. Our strategy enables precise, stepwise, and controllable regulation of MSIs, providing insights for the development of highly efficient and durable heterostructured catalysts with optimal MSI for a wide range of catalytic applications.