Solid-solid phase transitions are processes ripe for the discovery of correlated atomic motion in crystals. Here, we monitor an order-disorder transition in real-time in nanoparticles of the super-ionic solid, Cu_2-xSe. The use of in-situ high-resolution transmission electron microscopy allows the spatiotemporal evolution of the phase transition within a single nanoparticle to be monitored at the atomic level. The high spatial resolution reveals that cation disorder is nucleated at low co-ordination, high energy sites of the nanoparticle where cationic vacancy layers intersect with surface facets. Time-dependent evolution of the reciprocal lattice of individual nanoparticles shows that the initiation of cation disorder is accompanied by a ~3% compression of the anionic lattice, establishing a correlation between these two structural features of the lattice. The spatiotemporal insights gained here advance understanding of order-disorder transitions, ionic structure and transport, and the role of nanoparticle surfaces in phase transitions.

Ethylene epoxidation is used to produce 2 × 10⁷ ton per year of ethylene oxide, a major feedstock for commodity chemicals and plastics. While high pressures and temperatures are required for the reaction, plasmonic photoexcitation of the Ag catalyst enables epoxidation at near-ambient conditions. Here, we use surface-enhanced Raman scattering to monitor the plasmon excitation-assisted reaction on individual sites of a Ag nanoparticle catalyst. We uncover an unconventional mechanism, wherein the primary step is the photosynthesis of graphene on the Ag surface. Epoxidation of ethylene is then promoted by this photogenerated graphene. Density functional theory simulations point to edge defects on the graphene as the sites for epoxidation. Guided by this insight, we synthesize a composite graphene/Ag/α-Al₂O₃ catalyst, which accomplishes ethylene photo-epoxidation under ambient conditions at which the conventional Ag/α-Al₂O₃ catalyst shows negligible activity. Our finding of in situ photogeneration of catalytically active graphene may apply to other photocatalytic hydrocarbon transformations.