A new form of surfactant-free microemulsion (SFME) including hydrophobic deep eutectic solvent (HDES)/ethanol/water was constructed based on its CO2 response, and three regions, that is, HDES-in-water (HDES/W), bicontinuous (B.C.), and water-in-HDES (W/HDES) regions, were recognized. It is anticipated that SFMEs with tunable microstructures have outstanding applications as nanoreactors in reaction processes. The feasibility of preparing nanoparticles from HDES/ethanol/water SFME using barium fluoride (BaF2) as a model nanoparticle was investigated. HDES-based microemulsions benefit from HDES's excellent properties (novel, low toxicity, CO2-responsive, easy availability) and have potential in universal reactions, drug delivery, advanced material fabrication, etc. In this research, HDES-based microemulsions were prepared using HDES as the oil phase. Phase equilibria and microstructure were investigated using a ternary phase diagram, UV spectrophotometry, and the conductivity method. The CO2 switchable characteristics of the HDES-based microemulsions were investigated. HDES-based microemulsions were proposed as nanoreactors for the synthesis of barium fluoride nanomaterials. The microemulsion structure can modulate the size, morphology, and physicochemical properties of the nanoparticles through the CO2 switchable properties. It is argued that nanoreactors constructed with versatile HDES will offer a new direction for creation of cutting-edge scientific applications.
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