Quantitative Characterization of the Thermally Driven Alloying State in Ternary Ir-Pd-Ru Nanoparticles

XQ Tran and K Aso and T Yamamoto and WH Yang and Y Kono and K Kusada and DS Wu and H Kitagawa and S Matsumura, ACS NANO, 16, 1612-1624 (2022).

DOI: 10.1021/acsnano.1c10414

Compositional and structural arrangements of constituent elements, especially those at the surface and near-surface layers, are known to greatly influence the catalytic performance of alloyed nanoparticles (NPs). Although much research effort often focuses on the ability to tailor these important aspects in the design stage, their stability under realistic operating conditions remains a major technical challenge. Here, the compositional stability and associated structural evolution of a ternary iridium-palladium-ruthenium (Ir-Pd-Ru) nanoalloy at elevated temperatures have been studied using interrupted in situ scanning transmission electron microscopy and theoretical modeling. The results are based on a combinatory approach of statistical sampling at the subnanometer scale for large groups of NPs as well as tracking individual NPs. We find that the solid solution Ir-Pd-Ru NPs (similar to 5.6 nm) evolved into a Pd-enriched shell supported on an alloyed Ir-Ru- rich core, most notably when the temperature exceeds 500 degrees C, concurrently with the development of expansive atomic strain in the outer surface and subsurface layers with respect to the core regions. Theoretically, we identify the weak interatomic bonds, low surface energy, and large atomic sizes associated with Pd as the key factors responsible for such observed features.

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