Fluorine Doping of Microporous Organosilica Membranes for Pore Size Control and Enhanced Hydrophobic Properties

[Image: see text] Fluorine-doped organosilica membranes for gas and pervaporation (PV) separation were fabricated using a sol–gel method. NH(4)F and bis(triethoxysilyl)methane (BTESM) were selected as the dopant and Si precursor, respectively, for the fabrication of fluorine-doped organosilica membranes. Doping with fluorine was evaluated for its effect on the physicochemical properties of organosilica (hydrophobicity/hydrophilicity and network size). Fluorine doping dramatically eliminated the formation of Si–OH groups in the sol, so that the condensation of Si–OH groups during the calcination process was suppressed. It is possible that fluorine doping enlarged the network pore sizes in organosilica, because the F-BTESM (F/Si = 1/9) membrane showed superior He and H(2) permeance with a low H(2)/N(2) permeance ratio that corresponded to the network pore size by comparison with an undoped BTESM membrane. The F-BTESM (F/Si = 1/9) membranes clearly showed a high level of C(3)H(6) permeance (>3.0 × 10(–7) mol m(–2) s(–1) Pa(–1)) with a high C(3)H(6)/SF(6) permeance ratio (∼250), which suggests that the network pore size of F-BTESM is suitable for the separation of large molecules such as hydrocarbon gases (C3/C4, C4 isomer, etc.). Organosilica membranes both with and without fluorine doping showed stable PV performance because of the fact that H(2)O permeance and each permeance ratio under different separation systems was approximately constant over 10 h at 70 °C. Fluorine doping enhanced the hydrophobic nature of the organosilica, which was confirmed by the H(2)O adsorption and PV properties.