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Charge Properties of TiO2 Nanotubes in NaNO3 Aqueous Solution

Špadina, Mario; Gourdin-Bertin, Simon; Dražič, Goran; Selmani, Atiđa; Dufrêche, Jean-François; Bohinc, Klemen (2018) Charge Properties of TiO2 Nanotubes in NaNO3 Aqueous Solution. ACS Applied Materials and Interfaces, 10 (15). pp. 13130-13142. ISSN 1944-8244

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Charging of material surfaces in aqueous electrolyte solutions is one of the most important processes in the interactions between biomaterials and surrounding tissue. Other than a biomaterial, titania nanotubes (TiO2 NTs) represent a versatile material for numerous applications such as heavy metal adsorption or photocatalysis. In this article, the surface charge properties of titania NTs in NaNO3 solution were investigated through electrophoretic mobility and polyelectrolyte colloid titration measuring techniques. In addition, we used high-resolution transmission electron microscopy imaging to determine the morphology of TiO2 NTs. A theoretical model based on the classical density functional theory coupled with the charge regulation method in terms of mass action law was developed to understand the experimental data and to provide insights into charge properties at different physical conditions, namely, pH and NaNO3 concentration. Two intrinsic protonation constants and surface site density have been obtained. The electrostatic properties of the system in terms of electrostatic potentials and ion distributions were calculated and discussed for various pH values. The model can quantitatively describe the titration curve as a function of pH for higher bulk salt concentrations and the difference in the equilibrium amount of charges between the inner and outer surfaces of TiO2 NTs. Calculated counterion (NO3–) distributions show a pronounced decrease of NO3– ions for high bulk pH (both inside and outside TiO2 NT) because of the strong electric field. With the decrease of bulk pH or the increase of the salt concentration, NO3– is able to accumulate near the TiO2 NTs surfaces.

Item Type: Article
Additional Information: The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. [320915] "REE-CYCLE": Rare Earth Element reCYCling with Low harmful Emissions. The authors thank the Research Agency for support through grant BI-FR/CEA/16-18-002 and the Slovenian Research Agency for support through program P3-0388. The authors thank B. Siboulet and T. Zemb for useful discussions, to R. Fink for the assistance in using PCD, and Aurelio Barbetta for the software technical support.
Uncontrolled Keywords: adsorption ; charge ; distribution ; electrostatic ; HR-TEM ; mobility ; Poisson−Boltzmann ; polyelectrolyte ; potential
Subjects: NATURAL SCIENCES > Chemistry
NATURAL SCIENCES > Chemistry > Physical Chemistry
Divisions: Division of Physical Chemistry
Depositing User: Atiđa Selmani
Date Deposited: 03 Dec 2019 11:29
DOI: 10.1021/acsami.7b18737

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