Single-nanocrystal reaction trajectories reveal sharp cooperative transitions

Whereas pathways of chemical reactions involving small molecules are well-understood, the dynamics of reactions in extended solids remain difficult to elucidate. Frequently, kinetic studies on bulk materials provide a picture averaged over multiple domains or grains, smearing out interesting dynamics such as critical nucleation phenomena or sharp phase transitions occurring within individual, often nanoscale, grains, or domains. By optically monitoring a solid-state reaction with single nanocrystal resolution, we directly identified a unique, previously unknown, reaction pathway. Reaction trajectories of single cadmium selenide nanocrystals undergoing ion exchange with silver reveal that each individual nanocrystal waits a unique amount of time before making an abrupt switch to the silver selenide phase on a few hundred millisecond time scale. The gradual reaction progress of ensemble-scale cation exchange is actually comprised of these sharp single-nanocrystal switching events. Statistical distributions of waiting times suggest that the reaction is a cooperative transition rather than a diffusion-limited cation-by-cation exchange, which is confirmed by a stochastic reaction model. Such insight, achievable from single nanocrystal reaction studies, furthers mechanistic understanding of heterogeneous reactions, solid-state catalysis, bottom-up nanostructure growth, and materials' transformations and degradation in reactive environments.