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We analyzed the adsorption states of europium aqua ions (Eu3+) on mesoporous silicas with different pore distributions in comparison with nonporous silica using time-resolved laser-induced fluorescence spectroscopy. The parallel factor analysis was used to differentiate the contribution of different chemical species of Eu3+ to the fluorescence signal and determine the influence of the pore size on each chemical species. The results show that Eu3+ mainly form outer-sphere complexes with silica below pH 6, where Eu3+ adsorption is low. Within nano-sized pores, distortion of the hydration structure and a decrease in the hydration number were suggested in this pH range. As the concentration of the silicate ions derived from the dissolution of silica increases with increasing pH, Eu3+ form the silica/Eu3+/silicate ternary surface complexes. Within nano-sized pores, the concentration of silicate ions decreases due to the overlap of the electric double layer, which inhibits the formation of the ternary surface complex. Furthermore, at high pH, Eu3+ multinuclear complexes formed only on the mesoporous silica surface. This adsorption behavior specific to nano-sized pores could not be concluded by macroscopic adsorption experiments alone because the amount of Eu3+ adsorbed per unit surface area did not differ between the mesoporous and nonporous silicas. Consideration of the silicate complexes should be indispensable in future studies on the adsorption of lanthanide ions using mesoporous silica. Murota, K., Aoyagi, N., Mei, H., Saito, […]

by Murota & Saito Water in confinement becomes more structured than bulk water, and its properties, such as the dielectric constant, change. It remains unclear, however, how the interfacial reactions in confinement, such as the adsorption of ions on the surfaces of small pores, differ from those in larger spaces. We focused on the deprotonation reaction of hydroxyl groups, a fundamental surface reaction, and investigated the dependence of the surface charge density on pore size by determining the surface charge densities of six types of mesoporous silicas with micropores and mesopores at different ionic strengths and pH levels from batch titration tests. The surface complexation model assuming a potential distribution based on the Poisson-Boltzmann equation in cylindrical coordinates was fitted to the obtained surface charge densities to relate the electrostatics near the surface to the surface reaction. The results showed that the absolute values of the surface charge densities decreased with decreasing pore diameter due to the overlap of the electrical double layers. Furthermore, the capacitance of the Stern layer optimized by fitting decreased with decreasing pore diameter, especially in pores smaller than 4 nm in diameter, which suggested that the dielectric constants of water decreased near the surfaces of small pores. Murota, K.*, Saito, T., “Pore size effects on surface charges and interfacial electrostatics of mesoporous silicas”, Phys. Chem. […]