The development of robust and efficient porous adsorbents is essential for capturing xenon (Xe) and perfluorinated electron specialty gases (F-gases) in semiconductor exhaust gases, as toxic and corrosive gases coexist in high-temperature plasma degradation off-gases. Herein, two three-dimensional (3D) fluorinated porous aromatic frameworks (PAFs) with abundant fluorine (labeled PAF-4F and PAF-8F) were synthesized. The two PAFs exhibit high IAST selectivity in capturing Xe and F-gases from semiconductor off-gases, as well as excellent physicochemical stability and reusability, which have been collaboratively verified by single-component gas adsorption and regeneration tests, etc. Density functional theory (DFT) simulation revealed that the entry of strongly electronegative fluorine atoms into PAFs causes localized charge separation on the polymer pore surface, resulting in the preferential adsorption of high-polarizability Xe and F-gases via induced electric field gradients. Systematic studies have sufficiently manifested the great potential of fluorine-functionalized porous materials to effectively capture Xe and F-gases, which provides practical insights into the fabrication of highly stable porous adsorbents for harsh operating conditions.
Keywords: Xe/Kr; adsorption separation; fluorine functionalization; gas adsorption; porous aromatic framework.