Using a surface complexation model to predict the nature and stability of nanoparticles

Nanoparticles are discrete nanometer-scale assemblies of atoms and have dimensions between those characteristic of ions and those of macroscopic materials. These minerals commonly possess extremely large specific surface areas and surface adsorption capacities for foreign ions. Due to the large specific surface area and large fraction of surface atoms, the natures of nanoparticles are expected to be modified by the adsorption (surface complexation) process. In this paper,we discuss theoretically the stability of nanoparticles that make the surface complex with foreign ions. The principal theoretical assumption is that the surface complexation occurs at the bulk of the nanoparticles, as in a solid solution. The surface complexation affects two aspects of the intrinsic stability of the nanoparticles simultaneously: one is the composition of the nanoparticles; the other is the free energy of formation of nanoparticles. The solubility of hydrous ferric oxide (HFO) was estimated by using surface complexation modeling coupled with published data of the free energy of formation of the relevant components. The solubility modeling of surface-charged (H+ or OH- sorbed) HFO mechanistically and quantitatively explained the observed nonintegral behavior of the solubility of HFO. Moreover, solubility modeling of anion (SO4(2-), PO4(3-), and As(V)) sorption by HFO showed that the sorption process strongly influences the stability of the nanoparticles. This result implies that geochemical modeling leads to the erroneous prediction of a natural system if the effect of the sorption process is not taken into account.