Macroscopic 3D Nanoporosity Formation by Dry Oxidation of AgAu Alloys

3D nanoporous metals made by alloy corrosion have attracted much attention due to various promising applications ranging from catalysis and sensing to energy storage and actuation. In this work we report a new process for the fabrication of 3D open nanoporous metal networks that phenomenologically resembles the nano-Kirkendall hollowing process previously reported for Ag/Au nanowires and nanoparticles, with the difference that the involved length scales are 10–100 times larger. Specifically, we find that dry oxidation of Ag₇₀Au₃₀ bulk alloy samples by ozone exposure at 150 °C stimulates extremely rapid Ag outward diffusion toward the gas/alloy-surface interface, at rates at least 5 orders of magnitude faster than predicted on the basis of reported Ag bulk diffusion values. The micrometer-thick Ag depleted alloy region thus formed transforms into a 3D open nanoporous network morphology upon further exposure to methanol–O₂ at 150 °C. These findings have important implications for practical applications of alloys, for example as catalysts, by demonstrating that large-scale compositional and morphological changes can be triggered by surface chemical reactions at low temperatures, and that dilute alloys such as Au₉₇Ag₃ are more resilient against such changes