Sorption of Eu(III) onto titanium dioxide: Measurements and modeling

In the present study, the sorption of europium and lutetium onto titanium dioxide from aqueous solutions is presented, as a function of pH, ionic strength and concentration. An acid base model for the titanium dioxide surface was determined from potentiometric titrations and zeta-potential measurements. The common intersection point of potentiometric titrations coincided with the isoelectric point from electrokinetic experiments, resulting in a pristine point of zero charge of about 6.1. The experimental data were in agreement with previously published results and a previously published MUSIC-type model was used as the basis to model the acid-base behavior. Comparison of europium and lutetium showed no difference in the adsorption behavior. Furthermore, no difference was observed both in uptake and spectroscopic studies whether carbonate was absent or present. The absence of a noticeable effect of the ionic strength on the adsorption behavior was indicative of strong binding. EXAFS revealed rough conservation of the coordination with 9-8 water and surface hydroxyl groups upon sorption. EXAFS results suggested the existence of different metal-oxygen distances, more varied than that observed for the respective aquo complex and thus indicative for inner-sphere surface complexation. A clear differentiation of surface complexation denticity was not possible based on spectroscopic data. A multisite surface complexation model approach was applied by assuming monodentate and multidentate binding to describe the trivalent metal uptake data. It is conceivable that mono- and multidentate species contribute to lanthanide sorption to titanium dioxide. In other words a distribution of states occurs in cation surface complexation reactions

Observation and Alteration of Surface States of Hematite Photoelectrodes

Hematite prepared by atomic layer deposition (ALD) was found to exhibit photocurrents when illuminated by near-infrared light (lambda = 830 nm), whose energy is smaller than the band gap of hematite. The phenomenon was inferred to be a result of valence band to surface state transition. The influence of surface states on the thermodynamics of the hematite/water interface was studied under open-circuit conditions. It was discovered that the equilibrium potential of the hematite surface was more negative than water oxidation potential by at least 0.4 V. With a NiFeOx coating by photochemical decomposition of organometallic precursors, the equilibrium potential of hematite was restored to water oxidation potential, and the photoresponse under 830 nm illumination was annihilated. Therefore, the states were rationalized by the chemical status at the electrode surfaces, and this hypothesis was supported by similar observations on other metal oxide electrodes such as TiO2clos