Escape from the destruction of the galvanic replacement reaction for solid → hollow → solid conversion process in one pot reaction

Abstract

Based on the difference in the redox potentials between two metal species, the galvanic replacement reaction is known to create an irreversible process to generate hollow nanostructures in a wide range of shapes. In the context of galvanic replacement reaction, continuing etching leads to the general collapse of the hollow structures because of the excess amount of oxidizing agent. We demonstrate the growth of solid nanostructures from a hollow frame-like architecture in the course of a galvanic replacement reaction without any morphology destruction. We report the successful composition transformation of solid Ag with a wide range of shapes, such as plate, decahedron, rod, prism, sphere, and foil, from as thin as <10 nm up to 5 μm and with an area of ∼4 mm², to their solid Au counterparts using straightforward chemical reactions. The successful conversion process relies on a decrease in the reduction rate of the metallic precursor to initiate dissolution of Ag in the first stage (a galvanic replacement reaction), then a subsequent backfilling of Au into the hollowed-out structures. Cetyltrimethylammonium bromide (CTAB) surfactant, a key parameter, interacts with metal salt precursor to form a complex species that retards metal reduction. In addition, we demonstrate conversion of solid nano-Ag to solid nano-Pd as well as of Cu foil (10 μm thick) to shiny Au foil.