<p>Understanding and controlling the
formation of nanoparticles at the surface of functional oxide supports is
critical for tuning activity and stability for catalytic and energy conversion
applications. Here we use a latest generation environmental transmission
electron microscope to follow the exsolution of individual nanoparticles at the
surface of perovskite oxides, with unprecedented spatial and temporal resolution.
Qualitative and quantitative analysis of the data reveals the atomic scale
processes that underpin the formation of the socketed, strain-inducing
interface that confers exsolved particles their unique stability and
reactivity. This insight also enabled us to discover that the shape of exsolved
particles can be controlled by changing the atmosphere in which exsolution is
carried out and additionally, this could also produce intriguing new
heterostructures consisting of metal-metal oxide coupled nanoparticles. Our
results not only provide insight into the <i>in situ</i> formation of
nanoparticles, but also exemplify new dimensions for tailoring nanostructures
and nano-interfaces.</p>