Dual-Responsive Hybrid Microgels Enabling Phase Inversion in Pickering Emulsions

Pickering emulsions have emerged as promising multiphase systems owing to their high stability and diverse applications in materials and chemical engineering. However, achieving precise and stimuli-responsive regulation of emulsion type, particularly reversible phase inversion between oil-in-water and water-in-oil states under fixed formulation without additional stabilizers, remains a considerable challenge. In this work, we developed a sol-gel strategy, i.e., in situ hydrolysis and condensation of silane precursors to form a silica shell directly on responsive microgels, to produce H-SiO₂@P(NIPAM-co-MAA) hybrid microgels. The resulting hybrid particles simultaneously retained pH and temperature responsiveness, enabling the transfer of these properties from the polymeric network to the emulsion interface. When employed as stabilizers, the hybrid microgels allowed the controlled formation of Pickering emulsions that remained stable for one week under testing conditions. More importantly, they facilitated in situ reversible phase inversion under external stimuli. Overall, this work establishes a sol-gel approach to fabricate organic-inorganic hybrid microgels with well-defined dispersion and uniform silica deposition, while preserving dual responsiveness and enabling controlled phase inversion of Pickering emulsions.