Harnessing Thermodynamically Driven Restructuring for Ultra‐Stable Catalysts

ABSTRACT Heterogeneous catalysts often deactivate at high temperatures due to thermodynamic restructuring into more stable phases. Herein, we transform this typically detrimental process into a constructive design principle for ultra‐stable catalysts. This is achieved by strategically constructing homologous‐heterovalent interfaces, such as Ce 4+ /Ce 3+ heterointerfaces, through the controlled integration of two solid phases formed during high‐temperature restructuring of Ce‐based oxides. Within these interfaces, the amplified strain directly promotes the formation of single oxygen‐atom vacancies (SOVs), which efficiently activate the N─H bond in NH 3 . Consequently, the resulting cerium‐tantalum oxide catalysts exhibit outstanding activity for NO x reduction by NH 3 , even after severe hydrothermal aging at 1,100°C—a condition that deactivates conventional catalysts. The generality of this approach is demonstrated by extending it to lanthanum‐nickel oxide catalysts with tailored Ni 3+ /Ni 2+ heterointerfaces for CO oxidation, achieving sustained stability up to 1,100°C. These findings establish a general design concept to overcome the persistent activity‐stability trade‐off in heterogeneous catalysis.