Balsam-Pear-Skin-Like Porous Polyacrylonitrile Nanofibrous Membranes Grafted with Polyethyleneimine for Postcombustion CO2 Capture.

Amine-containing sorbents have been extensively studied for postcombustion carbon dioxide (CO2) capture because of their ability to chemisorb CO2 from the flue gas. However, most sorbents are in the form of powders currently, which is not the ideal configuration for the flue gas separation because of the fragile nature and poor mechanical properties, resulting in blocking of the flow pipes and difficult recycling. Herein, we present a novel approach for the facile fabrication of flexible, robust, and polyethyleneimine-grafted (PEI-grafted) hydrolyzed porous PAN nanofibrous membranes (HPPAN-PEI NFMs) through the combination of electrospinning, pore-forming process, hydrolysis reaction, and the subsequent grafting technique. Excitingly, we find that all the resultant porous PAN (PPAN) fibers exhibit a balsam-pear-skin-like porous structure due to the selective removal of poly(vinylpyrrolidone) (PVP) from PAN/PVP fibers by water extraction. Significantly, the HPPAN-PEI NFMs retain their mesoporosity, as well as exhibit good thermal stability and prominent tensile strength (11.1 MPa) after grafting, guaranteeing their application in CO2 trapping from the flue gas. When exposed to CO2 at 40 °C, the HPPAN-PEI NFMs show an enhanced CO2 adsorption capacity of 1.23 mmol g-1 (based on the overall quantity of the sample) or 6.15 mmol g-1 (based on the quantity of grafted PEI). Moreover, the developed HPPAN-PEI NFMs display significantly selective capture for CO2 over N2 and excellent recyclability. The CO2 capacity retains 92% of the initial value after 20 adsorption-desorption cycle tests, indicating that the resultant HPPAN-PEI NFMs have good long-term stability. This work paves the way for fabricating NFM-based solid adsorption materials endowed with a porous structure applied to efficient postcombustion CO2 capture.