Direct Imaging of the Atomic Mechanisms Governing the Growth and Shape of Bimetallic Pt-Pd Nanocrystals by In Situ Liquid Cell STEM.

Understanding the atomic mechanisms governing the growth of bimetallic nanoalloys is of great interest for scientists. As a promising material for photocatalysis applications, Pt-Pd bimetallic nanoparticles (NPs) have been in the spotlight for many years due to their catalytic performance, which is typically superior to that of pure Pt NPs. In this work, we use in situ liquid cell scanning transmission electron microscopy to track the exact atomic mechanisms governing the formation of bimetallic Pt-Pd NPs. We find that the formation process of the bimetallic Pt-Pd is divided into three stages. First, the nucleation and growth of ultrasmall primary nanoclusters are formed by the agglomeration of Pt and Pd atoms. Second, the primary nanoclusters are involved in a coalescence process to form two types of bigger agglomerates, namely, amorphous (a-NC) and crystalline (c-NC) nanoclusters. In the third stage, these clusters undergo a coalescence process leading to the formation of Pt-Pd NPs, while, in parallel, monomer attachment continues. We found that the third stage contains three types of coalescence processes, a-NC-a-NC, a-NC-c-NC, and c-NC-c-NC coalescence, which eventually give rise to crystalline bimetallic alloys. However, each type of coalescence gave distinct NPs in terms of shape and defects. Our results thus reveal the exact growth mechanisms of bimetallic alloys on the atomic scale, unravel the origin of their structure, and overall are of key interest to tailor the structure of bimetallic NPs.