Engineering Morphologies of Metal-Based Colloidal Assemblies via Colloid Jamming at Liquid-Liquid Interfaces

Self-assemblies, structured via nanoparticles, show promise as materials for advanced applications, like photonic devices, electrochemical energy storage units and catalysis support. Despite observing diverse morphologies, a comprehensive understanding of the formation mechanism remains elusive. In this work, we show that the coordination interaction between metal-based sulfide nanoparticles (MS NPs) and the fluorosurfactants at the droplet interface influences the morphology during the evaporation-induced self-assembly facilitated by droplet microfluidics. Further investigation into fluorosurfactants with various chemical groups and MS NPs reveals that the strength of coordination interactions significantly influences assembly morphology. The interfacial interactions can be eliminated through coating a SiO2 layer on the metal-based colloid (M@SiO2 NPs). In addition, we demonstrate that the morphologies of the self-assemblies can be engineered via the coordination interactions between the MS NPs and fluorosurfactants, and by varying the concentrations of MS NPs. Utilizing these interfacial interactions, assemblies with core-shell and homogeneous distribution of binary nanoparticles were constructed. Our findings offer novel insights into the interfacial jamming of nanoparticles at the droplet interface through evaporation-induced self-assembly, and into the design of metal-based colloidal assemblies with diverse morphologies, crucial for developing novel functional assemblies for catalysis, plasmonic, and porous materials in a controlled manner.