Lilypad aggregation: localised self-assembly and metal sequestration at a liquid–vapour interface

Spatially resolved soft materials, such as vesicles and microgels, have shown promise as selective adsorbents and microscale reaction vessels. However, spatiotemporal control of aggregation can be difficult to achieve. In this study, nickel(ii) chloride and a dipyridyl oligo(urea) ligand were combined in a vapour-diffusion setup to produce a localised spheroidal aggregate at the liquid–vapour interface. This aggregate forms via the self-assembly and fusion of monodisperse colloids and grows until its weight is no longer counterbalanced by surface tension. A simple physical model reveals that this process, termed lilypad aggregation, is possible only for surface energies that favour neither bulk aggregation nor the growth of an interfacial film. These surface energies dictate the final size and shape of the aggregate and may be estimated through visual monitoring of its changing morphology. Lilypad aggregates sequester metal from the surrounding sol and can be collected manually from the surface of the liquid.