Structure of Hydrated Zn2+ at the Rutile TiO2 (110)-Aqueous Solution Interface: Comparsion of X-ray Standing Wave, X-ray Absorption Spectroscopy, and Density Functional Theory Results
Adsorption of Zn{sup 2+} at the rutile TiO2 (110)-aqueous interface was studied with Bragg-reflection X-ray standing waves (XSW), polarization-dependent surface extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations to understand the interrelated issues of adsorption site, its occupancy, ion-oxygen coordination and hydrolysis. At pH 8, Zn{sup 2+} was found to adsorb as an inner-sphere complex at two different sites, i.e., monodentate above the bridging O site and bidentate between two neighboring terminal O sites. EXAFS results directly revealed a four or fivefold first shell coordination environment for adsorbed Zn{sup 2+} instead of the sixfold coordination found for aqueous species at this pH. DFT calculations confirmed the energetic stability of a lower coordination environment for the adsorbed species and revealed that the change to this coordination environment is correlated with the hydrolysis of adsorbed Zn{sup 2+}. In addition, the derived adsorption locations and the occupancy factors of both sites from three methods agree well, with some quantitative discrepancies in the minor site location among the XSW, EXAFS, and DFT methods. Additional XSW measurements showed that the adsorption sites of Zn{sup 2+} were unchanged at pH 6. However, the Zn{sup 2+} partitioning between the two sites changed substantially, with an almost equal distribution between the two types of sites at pH 6 compared to predominantly monodentate occupation at pH 8.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
- Sponsoring Organization:
- Doe - Office Of Science
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 914159
- Report Number(s):
- BNL-78727-2007-JA; GCACAK; TRN: US200804%%319
- Journal Information:
- Geochim. Cosmochim. Acta, Vol. 70, Issue 16; ISSN 0016-7037
- Country of Publication:
- United States
- Language:
- English
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