Morphological transformations of silver nanoparticles in seedless photochemical synthesis

Photochemical synthesis is an easily controlled and reliable method for the fabrication of silver (Ag) nanoparticles with various morphologies. In this work, we have systematically investigated the seedless photochemical synthesis of anisotropic Ag nanoparticles with and without PVP as surface capping agent. The time evolution of anisotropic Ag nanoparticles during the synthesis process are studied using UV-visible spectra, optical images and transmission electron microscopy. The results show that the light irradiation precisely controls the start and termination of the reaction, and the presence or absence of PVP greatly affects the morphology evolution of anisotropic Ag nanoparticles. With PVP as the surface capping agent, Ag nanoparticles grow into decahedra or prism by the deposition of Ag atoms on {111} or {110} facets through epitaxial growth. However, a different morphology evolution could happen when Ag nanoparticle is synthesized without PVP as surface capping agent. In this case, Ag nanoparticles can fuse into the decahedrons through an edge-selective particle fusion mechanism, which involves attachment, rotation and realignment of Ag nanoparticles. This process was evidenced with HRTEM images at the different stages of the transformation from Ag colloid to decahedra nanoparticles. Oriented attachment and Ostwald ripening also play important role in the transformation process.