Faceted platinum alloy nanoparticles, in particular octahedral Pt-Ni, have been recognized as one of the most promising cathode catalysts for use in hydrogen fuel cells for their dramatically improved oxygen reduction reaction (ORR) activity compared to their spherical counterparts and pure Pt. These findings revealed significant catalytic structure-property correlations and suggested the importance of controlling the facet growth of nanoparticles to achieve the desired property. Although considerable success has been achieved in synthesizing faceted alloy nanoparticles after years of intensive research, these achievements were mostly empirical. A good knowledge of the growth pathway, which is essential to guide rational synthesis, is still lacking. The past decade has witnessed technological advances of in situ electron microscopy and its uses in obtaining the growth trajectory of pure metal nanoparticles. Compared with pure metals, the growth pathway of faceted alloy nanoparticles is more complicated. With multiple elements being involved, it is challenging to identify their behaviors, both individually as different elements and collectively as alloy components, during the particle growth.
Herein we report a combinational use of several cutting-edge in situ characterization techniques, including aberration-corrected scanning transmission electron microscopy (AC-STEM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and X-ray absorption spectroscopy (XAS), to study the growth process of octahedral Pt3Ni nanoparticles. By integrating the information obtained from these techniques, together with computational simulations, a clear pathway for the particle growth and facet formation is revealed. Results indicate the surface enriched Ni plays a significant role in controlling the octahedra development by mediating the CO adsorption on (111) and (001) facets of Pt3Ni nanoparticles. Our findings highlight the significance of advanced in situ techniques in researching catalyst preparation and morphology control, providing an insightful understanding in synthesizing shaped catalysts.