Ultrathin polyorganosilica membranes synthesized by oxygen-plasma treatment of polysiloxanes for H2/CO2 separation

Oxygen plasma treatment of polydimethylsiloxane (PDMS) induces an ultrathin polyorganosilica (POSi) layer (<10 nm) on top of a PDMS membrane, leading to excellent H2/gas separation properties and providing a rapid and scalable way to fabricate robust silica membranes compared with conventional high-temperature and time-consuming sol-gel methods. Here, we thoroughly investigate POSi membranes derived from poly (dimethylsiloxane-co-methylhydroxidesiloxane) (poly (DMS-co-MHOS)) containing -SiOH groups that can be more easily converted to silica networks than the -SiCH3 in PDMS. The effect of the polysiloxane structure and plasma treatment conditions (including plasma generating powers, oxygen flowrate, chamber pressure, and treatment time) on the silica chemistry, structure, and H2/CO2 separation properties are systematically determined to derive structure/property relationships. An optimized membrane exhibits H2 permeance of 880 GPU and H2/CO2 selectivity of 67 at 150 °C, superior to state-of-the-art polymeric membranes. The membrane retains H2/CO2 selectivity as high as 46 when challenged with simulated syngas containing 2.8 mol% water vapor at 150 °C, demonstrating the potential of these POSi membranes for practical applications.