Abstract
The separation of CO2 from N2 remains a highly challenging task in postcombustion CO2 capture processes, primarily due to the relatively low CO2 content (3-15%) compared to that of N2 (70%). This challenge is particularly prominent for carbon-based adsorbents that exhibit relatively low selectivity. In this study, we present a successfully implemented strategy to enhance the selectivity of composite aerogels made of reduced graphene oxide (rGO) and functionalized polymer particles. Considering that the CO2/N2 selectivity of the aerogels is affected on the one hand by the surface chemistry (offering more sites for CO2 capture) and fine-tuned microporosity (offering molecular sieve effect), both of these parameters were affected in situ during the synthesis process. The resulting aerogels exhibit improved CO2 adsorption capacity and a significant reduction in N2 adsorption at a temperature of 25 °C and 1 atm, leading to a more than 10-fold increase in selectivity compared to the reference material. This achievement represents the highest selectivity reported thus far for carbon-based adsorbents. Detailed characterization of the aerogel surfaces has revealed an increase in the quantity of surface oxygen functional groups, as well as an augmentation in the fractions of micropores (<2 nm) and small mesopores (<5 nm) as a result of the modified synthesis methodology. Additionally, it was found that the surface morphology of the aerogels has undergone important changes. The reference materials feature a surface rich in curved wrinkles with an approximate diameter of 100 nm, resulting in a selectivity range of 50-100. In contrast, the novel aerogels exhibit a higher degree of oxidation, rendering them stiffer and less elastic, resembling crumpled paper morphology. This transformation, along with the improved functionalization and augmented microporosity in the altered aerogels, has rendered the aerogels almost completely N2-phobic, with selectivity values ranging from 470 to 621. This finding provides experimental evidence for the theoretically predicted relationship between the elasticity of graphene-based adsorbents and their CO2/N2 selectivity performance. It introduces a new perspective on the issue of N2-phobicity. The outstanding performance achieved, including a CO2 adsorption capacity of nearly 2 mmol/g and the highest selectivity of 620, positions these composites as highly promising materials in the field of carbon capture and sequestration (CCS) postcombustion technology.