Quantification of MgO surface excess on the SnO_2 nanoparticles and relationship with nanostability and growth

摘要

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO_2 nanoparticles plays an important role in the system's energetics and stability. Using X-ray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO_2 with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO_2 nanoparticles stability.