A phosphonium ionic liquid is used as an activator of silanol groups to improve the surface functionalization of silica nanoparticles with fluorosilanes in supercritical CO 2 .Due to their excellent optical, electrical and mechanical properties as well as their unique advantages such as high surface area, nanoparticles can play a key role in many nanotechnology applications. 1,2 For example, significant R&D resources have been devoted to nanoparticle technology in diverse fields including electronic and biomedical devices, automotive parts, coatings, drug delivery, gene delivery, catalysis and polymers. [3][4][5][6][7][8][9][10][11][12][13][14] For several of these applications surface functionalization is an important requirement. For example, to change the polarity of the nanoparticles and promote dispersion in organic solvents or polymers chemical treatment by cation exchange or grafting using organosilanes has been extensively practiced. [15][16][17] In addition, surface functionalization has been used to improve the stability of the nanoparticles and avoid aggregation in various media. 18,19 Surface functionalization is typically carried out in the presence of organic solvents. In some instances and to make the process greener, supercritical CO 2 (scCO 2 ) has been used in place of conventional solvents. However, the grafting density tends to be relatively low. It has been reported that small amounts of a highly basic ionic liquid (<0.5 wt%) can generate silanoates on the surface of silica. We combine here the use of an ionic liquid in scCO 2 to increase the grafting density of fluorosilane on silica. The process results in doubling of the grafting densities with the resulting nanoparticles exhibiting CO 2 -philic behavior. In addition to the increased reactivity and higher grafting density the new process offers the following additional advantages: (i) this is a one-step process, (ii) the use of organic solvents is completely eliminated, (iii) the lengthy steps of purification and drying of the silica are replaced by dilution and filtration, (iv) the ionic liquid can be recovered and reused.We note that our process differs from previous reports using scCO 2 in that low pressures (80 instead of 400 bar) and less amounts of silane (only 10 wt% compared to a 3-10 times molar excess of the corresponding coupling agents used in the literature) are required. 20,21 In addition, previous reports utilizing scCO 2 were limited to dry, fumed silica instead of aqueous dispersions used in our approach. While the primary particles of fumed silica are small and comparable to that of colloidal silica, drying tends to lead to particle agglomeration.While the method can be applicable to different oxides we demonstrate it here using colloidal silica and three different fluorosilanes: (i) perfluorooctyl-methyldimethoxysilane (DMS), (ii) perfluorooctyl-trichlorosilane (TCS), and (iii) perfluorooctyltriethoxysilane (TES). Triphenyloctadecyltriphenylphosphonium iodide (C 18 P I − ) was used as the surface activator. The synthesi...