“…Nanoparticles have drawn considerable attraction for their broad applications in many scientific fields including physics, chemistry, medicine, materials sciences, and others. − Especially, metallic nanoparticles have shown great potential in the sense that their catalytic performance can be finely controlled based on growth conditions. Substantial efforts have been devoted to realizing their desired functional properties by controlling specific size, shape, and composition of the synthesized nanocrystals. − Recent studies have revealed that the classical monomer attachment process is not the only mechanism for nanocrystal growth, and that particle–particle interaction, i.e., coalescence, also plays a crucial role in determining the size, shape, and structure of the nanocrystals. − Therefore, the coalescence mechanism has been actively studied by theoretical calculations − as well as in situ measurements, ,,,,,, and it has been shown that a coalescence event can result in not only single-crystalline nanoparticles, but also (multiply) twinned structures. ,,,,− The twin or other grain boundary structures can be stably formed during the coalescence processes, introducing a substantial difference in the electronic structure at the surface. ,,, Since it can often be beneficial for catalytic performance, − a better understanding of the coalescence and twinning process is important for fine tailoring of the nanocrystal structure and related catalytic properties. Furthermore, most of the oxygen reduction reaction (ORR) electrocatalytic activity measurements can only detect ensemble averaged properties, losing valuable information from individual nanoparticles. − To manipulate the ORR activity at the atomic scale, it is required to fully map the 3D detail of local ORR properties from individual nanoparticles, which can be achieved by atomic-resolution 3D structural study.…”