Functionalized two-dimensional g-C3N4 nanosheets in PIM-1 mixed matrix membranes for gas separation

Abstract

The virtuous of two-dimensional (2D) nanomaterials in high aspect ratio and tunable surface functionality have geared towards their implementation in mixed matrix membranes (MMMs) for advanced gas separation. In this study, the effects of functionalized 2D nanosheets in the MMMs for gas separation were investigated. The graphitic carbon nitride (g-C3N4) nanosheets were modified with various functional groups namely sulfuric acid group, aliphatic amino group, aromatic amino group, and sulfonic group via four different synthesis approaches. Polymers of intrinsic microporosity (PIMs, e.g., PIM-1) was selected as the continuous polymer phase due to its intrinsic high permeability and comparable selectivity towards different gas pair. The sulfonic acid functionalized g-C3N4 MMMs (e.g., PIM-1/g-C3N4-D) imparted high separation properties ascribed to the great CO2 affinity induced by the sulfonic acid groups. In particular, PIM-1/g-C3N4-D (99:1) MMM demonstrated promising CO2 separation performance, with CO2 permeability of 3740 Barrer and CO2/N2 selectivity of 19.8. Moreover, at 5 wt% loading of g-C3N4-D, the H2/N2 and O2/N2 separation of the MMMs had exceeded the 2008 Robeson upper bound, thanks to the periodic triangular ultramicropores in g-C3N4 that favor precise sieving of small gases. These results pave the way in using the developed membranes in practical H2 purification, air separation and CO2 capture.