Diffusive flux of nanoparticles through chemically modified alumina membranes

Surface chemistry plays an important role in determining flux through porous media such as in the environment. In this paper diffusive flux of nanoparticles through alkylsilane modified porous alumina is measured as a model for understanding transport in porous media of differing surface chemistries. Experiments are performed as a function of particle size, pore diameter, attached hydrocarbon chain length and chain terminus, and solvent. Particle fluxes are monitored by the change in absorbance of the solution in the receiving side of a diffusion cell. In general, flux increases when the membranes are modified with alkylsilanes compared to untreated membranes, which is attributed to the hydrophobic nature of the porous membranes and differences in wettability. We find that flux decreases, in both hexane and aqueous solutions, when the hydrocarbon chain lining the interior pore wall increases in length. The rate and selectivity of transport across these membranes is related to the partition coefficient (K-p) and the diffusion coefficient (D) of the permeating species. By conducting experiments as a function of initial particle concentration, we find that KpD increases with increasing particle size, is greater in alkylsilane-modified pores, and larger in hexane solution than water. The impact of the alkylsilane terminus (-CH3, -Br, -NH2, -COOH) on permeation in water is also examined. In water, the highest KpD is observed when the membranes are modified with carboxylic acid terminated silanes and lowest with amine terminated silanes as a result of electrostatic effects during translocation.