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Negative Surface Energies of Nickel Ferrite Nanoparticles under Hydrothermal Conditions

The formation of nickel ferrite (NiFe2O4) nanoparticles under hydrothermal conditions has been modeled using a method that combines results of first-principle calculations, elements of aqueous thermochemistry, and experimental free energies of formation. The calculations predict negative formation energies for the (111) surfaces and positive free energies for the formation of bulk nickel ferrite. Based on classical nucleation theory, the combination of the negative surface and positive bulk energies yields thermodynamically stable nickel ferrite nanoparticles with sizes between 30 and 150 nm in the temperature range of 300 to 400 K under alkaline conditions. The surface and bulk energetics as well as the stability of the nickel ferrite nanoparticle as a function of temperature and pH are discussed.