Scalable size- and shape-selective purification of colloidal building blocks via excluded volume interactions.

Excluded-volume interactions, arising solely from steric constraints, play a crucial role in determining the structure, dynamics, and phase behaviour of colloidal suspensions. This is particularly important for non-spherical particles, where orientation-dependent effects also become significant. In this study, we employ depletion-driven phase separation to develop a scalable, size-selective method for purifying spherical and non-spherical colloidal clusters that exhibit an interplay of concave and convex surface areas. Phase diagrams of charge-stabilised polystyrene spheres ranging in size from 267 to 1008 nm demonstrate that the mixing-demixing transition occurs across a range of surfactant concentrations rather than at a single threshold. Taking advantage of this transition width enables the purification of a single component from binary mixtures at size ratios as low as 1.6 in a single step. When the same approach is applied to tetrameric colloidal clusters, these are enriched fifteenfold relative to uncoordinated spheres. Importantly, the efficiency of sorting depends not only on the effective size but also on the geometry of the aggregate. For instance, anisotropic, weakly fused clusters separate more efficiently than spherical aggregates because their concave surface curvature is reduced compared to unfused clusters. These findings establish excluded-volume-driven sorting as a practical and scalable route for purifying colloidal building blocks for hierarchical assembly.