Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA, Université de Montpellier, CNRS, ENSCM, BP 17171, F-30207 Bagnols-sur-Ceze , France.
Laboratory for Materials Chemistry , National Institute of Chemistry , SI-1000 Ljubljana , Slovenia.
ACS Appl Mater Interfaces. 2018 Apr 18;10(15):13130-13142. doi: 10.1021/acsami.7b18737. Epub 2018 Apr 5.
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 (TiO 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 NaNO 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 TiO 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 NaNO 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 TiO NTs. Calculated counterion (NO) distributions show a pronounced decrease of NO ions for high bulk pH (both inside and outside TiO NT) because of the strong electric field. With the decrease of bulk pH or the increase of the salt concentration, NO is able to accumulate near the TiO NTs surfaces.
在水相电解质溶液中,材料表面的带电过程是生物材料与周围组织相互作用的最重要过程之一。除了生物材料之外,二氧化钛纳米管 (TiO NTs) 也是一种多功能材料,可用于许多应用,例如重金属吸附或光催化。在本文中,通过电泳迁移率和聚电解质胶体滴定测量技术研究了 TiO NTs 在 NaNO 溶液中的表面电荷特性。此外,我们还使用高分辨率透射电子显微镜成像来确定 TiO NTs 的形态。基于经典密度泛函理论并结合质量作用定律的电荷调节方法,开发了一个理论模型来理解实验数据,并深入了解不同物理条件下的电荷特性,即 pH 和 NaNO 浓度。获得了两个内在的质子化常数和表面位密度。计算并讨论了不同 pH 值下系统的静电特性,包括静电势和离子分布。该模型可以定量描述高盐浓度下 pH 值对滴定曲线的影响,以及 TiO NTs 内外表面之间电荷平衡量的差异。计算出的抗衡离子 (NO) 分布表明,由于强电场的作用,在高 bulk pH(TiO NT 内外)时,NO 离子的分布显著减少。随着 bulk pH 的降低或盐浓度的增加,NO 能够在 TiO NTs 表面附近积累。