Reactivity of high-entropy alloy nanoparticles under O₂ studied by in situ transmission electron microscopy

The gas reactivity of high-entropy nanoalloys (HENAs) is an emerging area of research with significant potential for applications in catalysis, gas sensing, hydrogen storage, and corrosion resistance. Insights into the structure-reactivity relationships that dictate the behavior of HENAs in reactive gas environments are critical for optimizing their performance across these applications. However, understanding the complex structural attributes of HENAs, such as size, shape and structure in response to a gas stimulus, remains challenging because of the limited accessibility to methods capable of probing these attributes under in situ or operando conditions. Here, we performed aberration-corrected environmental gas scanning transmission electron microscopy (STEM) observations to investigate the atomic and chemical structures of quinary CoNiCuPtAu HENAs in response to pure oxygen exposure at atmospheric pressure and elevated temperatures. The nanoparticles were fabricated by pulsed laser deposition with a high degree of control over both size and composition. Atomic-scale STEM imaging combined with energy dispersive X-ray (EDX) spectroscopy at the single particle level revealed a complex structural and chemical evolution pathway for CoNiCuPtAu HENAs under oxygen at atmospheric pressure during progressive heating up to 700 °C. Notably, we have identified substantial mass transfers between nanoparticles accompanied by oxygen-induced demixing of components, nanovoid formation and the stabilization of platelet-like nanostructures crystallizing as a Co-Ni oxide solid solution.