Pore Structure Controllability and CO₂ Permeation Properties of Silica-Derived Membranes with a Dual-Network Structure

Abstract

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.

A Brief Overview of the Microstructural Engineering of Inorganic–Organic Composite Membranes Derived from Organic Chelating Ligands

“…A class I hybrid is such that the organic and inorganic matrices are linked by weak interactive forces, such as hydrogen and van der Waals bonding [58]. An example of class I hybrids is the interpenetrating polymer and inorganic networks (IPNs) expressed in the schematic image in Figure 5a [59]. In class II hybrids, on the other hand, the interaction between the inorganic and organic parts, which includes strong bonds such as covalent and ionocovalent bonds, serve to improve the inorganic matrix qualities including improved hydrothermal stability [60], pore size controllability, [61] targeted functionalization, [62], etc.…”