Combined small-angle and high energy wide-angle x-ray scattering measurements of nanoparticle size and structure permit interior strain and disorder to be directly observed in the realspace pair distribution function (PDF). PDF analysis showed that samples of ZnS nanoparticle with similar mean diameters (3.2 -3.6 nm) but synthesized and treated differently possess a dramatic range 2 of interior disorder. We used Fourier transform infra-red spectroscopy to detect the surface species and the nature of surface chemical interactions. Our results suggest that there is a direct correlation between the strength of surface-ligand interactions and interior crystallinity.
Due to the importance of clay minerals in metal sorption, many studies have attempted to derive mechanistic models that describe adsorption processes. These models often include several different types of adsorption sites, including permanent charge sites and silanol and aluminol functional groups on the edges of clay minerals. To provide a basis for development of adsorption models it is critical that molecular-level studies be done to characterize sorption processes. In this study we conducted X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) spectroscopic experiments on copper (II) sorbed on smectite clays using suspension pH and ionic strength as variables. At low ionic strength, results suggest that Cu is sorbing in the interlayers and maintains its hydration sphere. At high ionic strength, Cu atoms are excluded from the interlayer and sorb primarily on the silanol and aluminol functional groups of the montmorillonite or beidellite structures. Interpretation of the XAFS and EPR spectroscopy results provides evidence that multinuclear complexes are forming. Fitting of extended X-ray absorption fine structure spectra revealed that the Cu-Cu atoms in the multinuclear complexes are 2.65 Å apart, and have coordination numbers near one. This structural information suggests that small Cu dimers are sorbing on the surface. These complexes are consistent with observed sorption on mica and amorphous silicon dioxide, yet are inconsistent with previous spectroscopic results for Cu sorption on montmorillonite. The results reported in this paper provide mechanistic data that will be valuable for modeling surface interactions of Cu with clay minerals, and predicting the geochemical cycling of Cu in the environment.
Nanoparticles of certain materials can respond structurally to changes in their surface environments. We have previously shown that methanol, water adsorption, and aggregation-disaggregation can change the structure of 3 nm diameter zinc sulfide (ZnS).However, in prior observations of water-driven structure change, aggregation may also have taken place. Therefore, we investigated the structural consequences of water adsorption alone on anhydrous nanoparticles that were dried to minimize changes in aggregation. Using simultaneously collected small-and wide-angle x-ray scattering (SAXS/WAXS) data, we show that water vapor adsorption alone drives a structural transformation in ZnS nanoparticles in the temperature range 22 -40 ˚C. The transition kinetics are strongly temperature dependent, with an activation energy of 58.1 ± 9.8 kJ/mol, consistent with atom displacement rather than bond breaking. At 50 ˚C, aggregate restructuring occurred, increasing the transition kinetics beyond the rate expected for water adsorption alone. The observation of isosbestic points in the WAXS data suggests that the particles do not transform continuously between the initial and final structural state but rather undergo an abrupt change from a less ordered to a more ordered state.
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