Sen Tumcan, Barisik Murat
Department of Mechanical Engineering, Izmir Institute of Technology, Izmir, 35430, Turkey.
Sci Rep. 2019 Jan 15;9(1):137. doi: 10.1038/s41598-018-36487-w.
Mesoporous silica is an emerging technology to solve problems of existing and to support projected revolutionary applications ranging from targeted drug delivery to artificial kidney. However, one of the major driving mechanisms, electric charging of internal mesoporous surfaces, has not been characterized yet. In the nanoscale confinements of mesoporous structures made of pore throats and pore voids, surface charges diverge from existing theoretical calculations and show local variation due to two occurrences. First, when the size of pore throat becomes comparable with the thickness of ionic layering forming on throats' surfaces, ionic layers from opposite surfaces overlap so that ionic concentration on the surface becomes different than Boltzmann distribution predicts, and there will no longer be an equilibrium of zero electric potential at pore throat centers. Second, when this non zero potential inside throats becomes different than the potential of pore voids, ionic diffusion from void to throat creates axial ionic variation on surfaces. For such a case, we performed a pore level analysis on mesoporous internal surface charge at various porosities and ionic conditions. Pore parameters strongly affected the average internal charge which we characterized as a function of overlap ratio and porosity, first time in literature. Using this, a phenomenological model was developed as an extension of the existing theory to include nano-effects, to predict the average mesoporous internal surface charge as a function of EDL thickness, pore size and porosity.
介孔二氧化硅是一种新兴技术,可解决现有问题并支持从靶向给药到人工肾脏等一系列预计的革命性应用。然而,其主要驱动机制之一,即内部介孔表面的电荷化,尚未得到表征。在由孔道和孔隙组成的介孔结构的纳米尺度限制中,表面电荷与现有的理论计算结果不同,并且由于两种情况而呈现局部变化。首先,当孔道尺寸与在孔道表面形成的离子层厚度相当时,相对表面的离子层会重叠,使得表面上的离子浓度不同于玻尔兹曼分布所预测的,并且在孔道中心不再存在零电势平衡。其次,当孔道内部的这种非零电势与孔隙的电势不同时,离子从孔隙向孔道的扩散会在表面产生轴向离子变化。针对这种情况,我们在各种孔隙率和离子条件下对介孔内表面电荷进行了孔级分析。孔隙参数强烈影响平均内部电荷,我们首次在文献中将其表征为重叠率和孔隙率的函数。利用这一点,开发了一个现象学模型,作为现有理论的扩展以纳入纳米效应,用于预测平均介孔内表面电荷作为双电层厚度、孔径和孔隙率的函数。