Molecular Imprinting as a Tool for Exceptionally Selective Gas Separation in Nanoporous Polymers

Abstract

The alarming rise in atmospheric CO2 levels, primarily driven by fossil fuel combustion and industrial processes, has become a major contributor to global climate change. Effective CO2 capture technologies are urgently needed, particularly for the selective removal of CO2 from industrial gas streams, such as flue gas and biogas, which often contain impurities like N2 and CH4. In this study, we report the design and synthesis of novel molecularly imprinted polymers (MIPs) using 4-vinylpyridine (4VP) and methacrylic acid (MAA) as functional monomers, and thiophene (Th) and formaldehyde (HC) as molecular templates. The MIPs were specifically engineered to create selective molecular cavities within a nanoporous polymer matrix for the efficient capture of CO2. By adjusting the molar ratios of the template to functional monomers, we optimized the molecular imprinting process to enhance CO2 selectivity over N2 and CH4. The resulting MIPs exhibited outstanding performance, with a maximum CO2/N2 selectivity of 153 at 25 bar and CO2/CH4 selectivity of 25.3 at 1 bar, significantly surpassing previously reported porous polymers and metal-organic frameworks (MOFs) under similar conditions. Furthermore, we conducted heat of adsorption studies, which revealed the strong and selective interaction of CO2 with the imprinted cavities, confirming the superior adsorption properties of the synthesized MIPs. The study demonstrates that molecular imprinting can effectively enhance both CO2 capture capacity and selectivity, providing a cost-efficient and scalable solution for industrial CO2 separation and purification processes.