Squeezing Out Nanoparticles from Perovskites: Controlling Exsolution with Pressure

Abstract

AbstractNanoparticle exsolution has emerged as a versatile method to functionalize oxides with robust metallic nanoparticles for catalytic and energy applications. By modifying certain external parameters during thermal reduction (temperature, time, reducing gas), some morphological and/or compositional properties of the exsolved nanoparticles can be tuned. Here, it is shown how the application of high pressure (<100 bar H2) enables the control of the exsolution of ternary FeCoNi alloyed nanoparticles from a double perovskite. H2 pressure affects the lattice expansion and the nanoparticle characteristics (size, population, and composition). The composition of the alloyed nanoparticles could be controlled, showing a reversal of the expected thermodynamic trend at 10 and 50 bar, where Fe becomes the main component instead of Ni. In addition, pressure drastically lowers the exsolution temperature to 300 °C, resulting in unprecedented highly‐dispersed and small‐sized nanoparticles with a similar composition to those obtained at 600 °C and 10 bar. The mechanisms behind the effects of pressure on exsolution are discussed, involving kinetic, surface thermodynamics, and lattice‐strain factors. A volcano‐like trend of the exsolution extent suggests that competing pressure‐dependent mechanisms govern the process. Pressure emerges as a new design tool for metallic nanoparticle exsolution enabling novel nanocatalysts and surface‐functionalized materials.