Hierarchically Microstructured Supraparticles via Electrospraying for Structurally Stable and Multifunctional Liquid Marbles

Abstract Hierarchically microstructured supraparticles (HMSPs) are engineered through a scalable and environmentally benign electrospraying strategy to construct liquid marbles (LMs) with exceptional structural stability and multifunctionality. Fabricated directly from colloidal silica sol precursors without additional solvents or surfactants, the HMSPs exhibit submicron dimensions and hierarchical porosity, which endow them with superior liquid repellency and robust mechanical integrity. By correlating particle size of the colloidal silica sols, evaporation dynamics, and surface roughness with LMs performance, design principles are established that maximize LMs stability under impact and compression. Beyond mechanical stability, the LMs exhibit remarkable multifunctional capabilities, including controllable non‐spherical morphologies, multi‐droplet encapsulation, suction/infusion‐driven shape transformations, segmentation–reassembly behaviors, and the formation of stable air–liquid biphasic heterostructures. Leveraging this platform, an integrated LMs‐based water‐splitting system capable of continuous hydrogen and oxygen generation, transport, and stoichiometric gas collection is further demonstrated. This work highlights electrospraying as a green and versatile method for supraparticle fabrication and provides a rational framework for designing next‐generation LMs platforms for encapsulation, adaptive microfluidics, and microscale electrochemical applications.