Competitive adsorption of ZrO2 nanoparticle and alkali cations (Li+ – Cs+) on muscovite (001)

We studied the adsorption behavior of ZrO2 nanoparticles on muscovite (001) surface in the presence of cations from the alkali series (Li+, Na+, K+, Rb+ and Cs+). The results of surface X-ray diffraction, i.e. crystal truncation rod and resonant anomalous X-ray reflectivity in combination with AFM images, shows that the sorption of ZrO2 nanoparticles is significantly affected by the binding mode of alkali ions on the muscovite (001) surface. From solutions containing alkali ions binding as outer sphere surface complexes (i.e. Li+ and Na+), higher uptake of Zr4+ is observed corresponding to the binding of larger nanoparticles, which relatively easily replaces the loosely bound alkali ions. However, Zr4+ uptake in solutions containing alkali ions binding as inner sphere surface complexes (i.e. K+, Rb+, and Cs+) is significantly lower and smaller nanoparticles are found at the interface. In addition, uptake of Zr4+ in the presence of inner sphere bound cations displays a strong linear relationship with hydration energy of the coexisting alkali ion. The linear trend can be interpreted as competitive adsorption between ZrO2 nanoparticles and inner sphere bound alkali cations, which are replaced on the surface and undergo rehydration after release to the solution. The rehydration of alkali ion gives rise to a large energy gain, which dominates the reaction energy of the competitive adsorption process. The competitive adsorption mechanism of ZrO2 nanoparticle and alkali ions is discussed comprehensively to highlight the potential relationship between the hydration effect of alkali ions and the effect of charge density of the nanoparticles.