We proposed a novel method for designing
CO2 permselective
organosilica/polymer membranes with a dual-network structure composed
of silica (first) and alkylamine-based (second) networks to control
molecular sieving and CO2 adsorption properties in the
membrane. Organosilica/polymer membranes were fabricated using 1,2-bis(triethoxysilyl)ethane
(BTESE) or 1,2-bis(triethoxyailyl)acetylene (BTESA) as the first network,
with polyethylenimine (PEI) as the second network via the sol–gel
process. CO2 adsorption measurements of BTESE/PEI films
were conducted via in situ Fourier transform infrared
to evaluate the effects that different types of acid catalysts exert
on CO2 adsorption properties. The results showed that only
BTESE/PEI films prepared with a catalyst of acetic acid (HAc) display
impressive chemical reactions between CO2 and amine groups,
whereas the use of HCl may deactivate the amine groups. We found that
the gas permeation properties of organosilica/PEI membranes were greatly
dependent on the Si-precursor. Almost no selectivity could be confirmed
for BTESA/PEI membranes, although pure BTESA membranes did show molecular
sieving properties. However, BTESE/PEI membranes showed improved separation
performance compared with that of pure BTESE membranes due to a reduction
in the free volume (BTESE: H2/CH4 selectivity
< 100, BTESE/PEI: H2/CH4 > 100). Moreover,
the pore size of BTESE/PEI membranes could be controlled via the BTESE/PEI
ratio. In conclusion, we successfully designed a dual-network structure
with a controlled pore size via changes made to the Si-precursor and/or
to the Si-precursor/PEI mixing ratio.