Metal particles supported on oxide surfaces are used as catalysts for a wide variety of processes in the chemical and energy conversion industries. For catalytic applications, metal particles are generally formed on an oxide support by physical or chemical deposition, or less commonly by exsolution from it. Although fundamentally different, both methods might be assumed to produce morphologically and functionally similar particles. Here we show that unlike nickel particles deposited on perovskite oxides, exsolved analogues are socketed into the parent perovskite, leading to enhanced stability and a significant decrease in the propensity for hydrocarbon coking, indicative of a stronger metal–oxide interface. In addition, we reveal key surface effects and defect interactions critical for future design of exsolution-based perovskite materials for catalytic and other functionalities. This study provides a new dimension for tailoring particle–substrate interactions in the context of increasing interest for emergent interfacial phenomena.

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