Abstract
Indium oxide (In2O3) nanoparticles (NPs) are used in electronic devices, from which indium (as its nanoparticulate form or as other generated chemical species) can be released to natural waters. To assess for the impacts of such releases (e.g. toxic effects), information on the kinetics and thermodynamics of the In2O3 dissolution processes is key. In this work, the evolution with time of the dissolution process was followed with the technique AGNES (Absence of Gradients and Nernstian Equilibrium Stripping) by measuring the free indium concentration ([In3+]). AGNES can determine the free ion concentration in the presence of nanoparticles without a prior separation step, as shown in the case of ZnO nanoparticles, a procedure that is more accurate than the typical sequence of centrifugation+filtration+elemental analysis. Excess of indium oxide NPs were dispersed in 0.1 mol L−1 KNO3 at various pH values ranging from 2 to 8. Additional dispersions with bulk In2O3 at pH 3 or NPs in synthetic seawater at pH 8 were also prepared. The temperature was carefully fixed at 25 °C. The dispersions were continuously stirred and samples were taken from time to time to measure free indium concentration with AGNES. 180-day contact of In2O3 to solutions at pH 2 and 3 was not enough to reach equilibrium. The dissolution of the NPs at pH 3 was faster than that of the bulk (i.e. non nanoparticulate) material. Equilibrium of the NPs with the solution was reached at pH 4 and 5 in KNO3 and at pH 8 in seawater, in shorter times for higher pH values, with free indium concentrations decreasing by a factor of 1000 for each increase in one pH unit. The solubility products of In(OH)3 and In2O3 were compared. Equilibration of NPs with synthetic seawater took <18 days, with an average free [In3+] (up to 196 days) of 1.03 amol L−1.
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