Dispersion of Hydrophilic "Hedgehog" Microparticles in Liquid CO2 Mixtures.

Abstract

Liquid and supercritical CO2 are nontoxic and nonflammable reaction media with pressure-variable physical properties. These states of CO2 also have high solubility limits for gas and liquid hydrocarbons, making them good candidates for "green" hydrophobic solvents in sustainable chemical technologies. However, the dispersion of hydrophilic colloidal nanoscale and microscale particles in CO2 is challenging due to the tendency of polar particles to aggregate in nonpolar media, limiting their available surface area and catalytic efficiencies. Here we show that native hydrophilic semiconductor particles can be effectively dispersed in a liquid CO2 mixture with acetonitrile (ACN) without additional chemical or mechanical dispersion techniques. Using surface corrugation as a method to prevent aggregation, we find that geometrically complex particles with a halo of stiff nanoscale spikes disperse and remain suspended longer in liquid CO2 than those without or with less prominent nanoscale corrugation. For the particles of this size and liquid CO2 mixtures, individual particle mass remains a prominent factor determining particle sedimentation rate even in the absence of aggregation. Particle dispersion and structural stability are confirmed using a combination of UV-vis spectroscopy, finite-difference time-domain modeling, and electron microscopy. The necessity of the cosolvent (ACN) indicates that particle behavior in liquid CO2 is vastly different than in traditional liquid-phase solvents and highlights the need for future studies to understand the wetting behavior of hydrophilic particles in high-pressure nonpolar environments.