A nanoscale chemical oscillator: reversible formation of palladium nanoparticles in ionic liquid

Abstract

From the theory of chaos-to-order transitions to the origins of life on Earth, oscillating chemical reactions play a fundamental role in nature. This study demonstrates how chemical oscillators can exist at the nanoscale, bridging the gap between molecules and living cells. We identify three necessary conditions for nanoscale chemical oscillations: (i) a continuous energy flux; (ii) alternating fluxes of two chemical species with opposing effects—specifically, a reductant and an oxidant; and (iii) a redox-active metal. Irradiating palladium ions dissolved in benzyl imidazolium bromide ([BnMIm]⁺Br⁻) with a 200 keV electron beam meets these requirements, resulting in the oscillating, dendritic assembly of palladium nanoparticles. By encapsulating the solution inside carbon nanotubes, we can slow down the rate of chemical oscillations, allowing for real-time analysis at the individual nanoparticle level. Our results indicate that nanoparticles in liquids are far from the thermodynamic equilibrium during transmission electron microscopy (TEM) imaging, which is an important consideration for studying nanoparticles using in situ TEM methods or employing them for catalysis in the liquid phase.