Abstract
Adsorption of supercritical CO2 in nanoporous silica aerogel was investigated by a combination of experiments and molecular-level computer modeling. High-pressure gravimetric and vibrating tube densimetry techniques were used to measure the mean pore fluid density and excess sorption at 35 °C and 50 °C and pressures of 0-200 bar. Densification of the pore fluid was observed at bulk fluid densities below 0.7 g/cm3. Far above the bulk fluid density, near-zero sorption or weak depletion effects were measured, while broad excess sorption maxima form in the vicinity of the bulk critical density region. The CO2 sorption properties are very similar for two aerogels with different bulk densities of 0.1 g/cm3 and 0.2 g/cm3, respectively. The spatial distribution of the confined supercritical fluid was analyzed in terms of sorption- and bulk-phase densities by means of the Adsorbed Phase Model (APM), which used data from gravimetric sorption and small-angle neutron scattering experiments. To gain more detailed insight into supercritical fluid sorption, large-scale lattice gas GCMC simulations were utilized and tuned to resemble the experimental excess sorption data. The computed three-dimensional pore fluid density distributions show that the observed maximum of the excess sorption near the critical density originates from large density fluctuations pinned to the pore walls. At this maximum, the size of these fluctuations is comparable to the prevailing pore sizes.
