Abstract
Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) Crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl2 in NaCl, and trace ZnCl2 in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding
should predominate on low bulk dielectric constant oxides such as cassiterite (εbulk ≈ 11). Inner-sphere adsorption is also significant for Rbþ and Naþ on neutral surfaces, whereas Cl- binding is predominately outer-sphere. As negative surface charge increases, relatively more Rbþ, Naþ, and especially Sr2þ are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn2þ are very steep but similar for both oxides, reflective of Zn2þ hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOHþ on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere
binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner-sphere cation binding is relatively more favorable.