Departamento de Física Aplicada I, Facultad de Ciencias, Universidad de Málaga, E-29071 Málaga, Spain.
ACS Appl Mater Interfaces. 2013 May;5(9):3556-64. doi: 10.1021/am400300r. Epub 2013 Apr 25.
Nanoporous anodic alumina membranes (NPAMs) were produced by the two-step anodization method in sulphuric, oxalic and phosphoric acidic electrolytes displaying a hexagonally ordered spatial arrangement of pores with well controlled nanopore size distribution and low porosity. Some selected NPAMs were further modified by conformal coating their surface and inner pore walls with a thin layer of SiO2 by means of atomic layer deposition (ALD), which reduces both the pore radii and porosity but it also seems to affect to the electric fixed charge on the membranes surface. A comparative study about the influence of silica modification of NPAMs surfaces on the ionic transport through the nanoporous membranes has been performed by measuring membrane potentials and electrochemical impedance spectroscopy with NaCl solutions. According to these results, a direct correlation between the membrane effective fixed charge and the NaCl diffusion coefficient can be established. The coating with a SiO2 thin layer causes a reduction of 75% in the positive effective fixed charge of the NPAMs independently of their pore radii and the increase in counterion transport (cation transport number and diffusion coefficient) even through constrained nanopores, which can be of interest in several applications (microfluidics, drug delivery, nanofilter devices, etc.). Moreover, slight changes in the membrane/solution interface due to the SiO2 cover layer are also indicated.
纳米多孔阳极氧化铝膜(NPAMs)通过两步阳极氧化法在硫酸、草酸和磷酸电解液中制备,显示出具有良好控制的纳米孔尺寸分布和低孔隙率的六边形有序空间排列的孔。一些选定的 NPAMs 进一步通过原子层沉积(ALD)在其表面和内孔壁上进行薄的 SiO2 共形涂层来修饰,这降低了孔径和孔隙率,但似乎也会影响膜表面的固定电荷。通过测量带有 NaCl 溶液的膜电势和电化学阻抗谱,对 NPAMs 表面的二氧化硅修饰对纳米多孔膜中离子传输的影响进行了比较研究。根据这些结果,可以建立膜有效固定电荷与 NaCl 扩散系数之间的直接相关性。SiO2 薄层的涂层导致 NPAMs 的正有效固定电荷减少了 75%,而不管其孔径如何,以及反离子传输(阳离子迁移数和扩散系数)的增加,即使是通过受限的纳米孔,这在几种应用中可能是有趣的(微流控、药物输送、纳米过滤装置等)。此外,还表明由于 SiO2 覆盖层,膜/溶液界面发生了轻微变化。