Mapping the surface (hydr)oxo-groups of titanium oxide and its interface with an aqueous solution: the state of the art and a new approach.
In this article the "titanium oxide/electrolyte solution" interface is studied by taking in advantage the recent developments in the field of Surface and Interface Chemistry relevant to this oxide. Ab-initio calculations were performed in the frame of the DFT theory for estimating the charge of the titanium and oxygen atoms exposed on the anatase (1 0 1), (1 0 0), (0 0 1), (1 0 3)(f) and rutile (1 1 0) crystal faces. These orientations have smaller surface energy with respect to other ones and thus it is more probable to be the real terminations of the anatase and rutile nanocrystallites in the titania polycrystalline powders. Potentiometric titrations for obtaining "fine structured" titration curves as well as microelectrophoresis and streaming potential measurements have been performed. On the basis of ab-initio calculations, and taking into account the relative contribution of each crystal face to the whole surface of the nanocrystals involved in the titania aggregates of a suspension, the three most probable surface ionization models have been derived. These models and the Music model are then tested in conjunction with the "Stern-Gouy-Chapman" and "Basic Stern" electrostatic models. The finally selected surface ionization model (model A) in combination with each one of the two electrostatic models describes very well the protonation/deprotonation behavior of titania. The description is also very good if this model is combined with the Three Plane (TP) model. The application of the "A/(TP)" model allowed mapping the surface (hydr)oxo-groups [TiO(H) and Ti(2)O(H)] of titania exposed in aqueous solutions. At pH>pzc almost all terminal oxygens [TiO] are non-protonated whereas even at low pH values the non-protonated terminal oxygens predominate. The acid-base behavior of the bridging oxygens [Ti(2)O] is different. Thus, even at pH=10 the greater portion of them is protonated. The application of the "A/TP" model in conjunction with potentiometric titrations, microelectrophoresis and streaming potential experiments allowed mapping the "titania/electrolyte solution" interface. It was found that the first (second) charged plane is located on the oxygen atoms of the first (second) water overlayer at a distance of 1.7 (3.4) A from the surface. The region between the surface and the second plane is the compact layer. The region between the second plane and the shear plane is the stagnant diffuse part of the interface, with an ionic strength dependent width, ranging from 20 (0.01 M) up to 4 A (0.3 M). The region between the shear plane and the bulk solution is the mobile diffuse part, with an ionic strength dependent width, ranging from 10 (0.01 M) up to 2 A (0.3 M). At I>0.017 M the mean concentration of the counter ions is higher in the stagnant than in the mobile part of the diffuse layer. For a given I, removal of pH from pzc brings about an increase of the mean concentration in the interfacial region and a displacement of the counter ions from the mobile to the stagnant part of the diffuse layer. The mean concentration of the counter ions in the compact layer is generally lower than the corresponding ones in the stagnant and mobile diffuse layers. The mobility of the counter ions in the stagnant layer decreases as pH draws away from pzc or ionic strength increases.
Department of Chemistry, University of Patras, GR-265 00 Patras, Greece.
George D
GD
Panagiotou
Theano
T
Petsi
Kyriakos
K
Bourikas
Christos S
CS
Garoufalis
Athanassios
A
Tsevis
Nikos
N
Spanos
Christos
C
Kordulis
Alexis
A
Lycourghiotis
D004573:Electrolytes; D053768:Metal Nanoparticles / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D011522:Protons; D012996:Solutions; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
D004573:Electrolytes; D011522:Protons; D012996:Solutions; D014867:Water; C009495:titanium dioxide; D014025:Titanium; D010100:Oxygen