Pore Size and Porosity Dependent Zeta Potentials of Mesoporous Silica Nanoparticles

Mesoporous silica nanoparticles (MSNPs) are synthesized in the various forms of porous structures according to an application's needs, while their zeta potentials play a major role in their function. We show that variation in pore size and/or porosity yields a substantial decrease in MSNP zeta potential up to 25% lower than the theoretical zeta potential predictions for a flat surface at the corresponding ionic conditions in moderate pH range. By considering surface chemistry as a function of local ionic conditions (charge regulation), we calculated local zeta potentials around the MSNP which showed variation between pore openings and solid surfaces. Through a systematic study, we evaluated an average three-dimensional zeta potential for MSNPs with various conditions, based on the ratio of the area covered by pore openings to the rest of the MSNP surface area as a function of three-dimensional porosity and pore size. Results show that the high overlap of ionic layers inside the pores creates electric potentials close to zeta potential of the remaining surface, but large pore size and/or high ionic salt concentration yields divergence. We characterized the variation of MSNP zeta potential in terms of porosity (epsilon(3D)), pore size (D-pore), and ionic condition quantified by Debye length (lambda) and obtained unified behavior as a function of the nondimensional group of epsilon(3D)(D-pore/lambda). For epsilon(3D)(D-pore/lambda) 0.01, MSNP zeta potential remains similar to flat plate predictions, but it decreases by increasing epsilon(3D)(D-pore/lambda) value. The influence of pore entrances on surface zeta potential increases nonlinearly by the increase of porosity and/or decrease of EDL overlap, similar to a change of area to volume ratio. The current findings are important for the understanding and further control of mesoporous particle transport in various promising and groundbreaking applications such as targeted drug delivery.