Capture and separation of styrene/ethylbenzene from organic waste gas via optimizing pore electronegativity of <scp>UiO</scp> ‐66

Abstract Adsorptive separation of styrene/ethylbenzene is highly desirable for air purification and resource recovery because they frequently appear as the highest amounts of volatile organic compounds in plastic industrial effluents. However, their similar physical properties and low concentration pose significant challenges for developing efficient adsorbents. Herein, we adjust the pore electronegativity of UiO‐66 via introducing Lewis basic ‐NH 2 to induce preferential styrene adsorption. Compared with its isostructural UiO‐66‐X (X = H, NO 2 , Br, CF 3 ), UiO‐66‐NH 2 presents optimal separation potential and one‐step recovery of ethylbenzene in &gt;99.0% purity from their dynamic binary mixtures. GCMC and DFT‐D calculations combined with in situ Fourier transform infrared spectroscopy (FTIR) and near ambient pressure X‐ray photoelectron spectroscopy (NAP XPS) reveal that C–H···O and C–H···π interactions are observed for UiO‐66 adsorbing ethylbenzene and styrene, yet with stronger ethylbenzene binding. Differently, UiO‐66‐NH 2 possesses strong C–H···N interactions except C–H···O and C–H···π, affording overall stronger interactions with styrene over ethylbenzene, thus realizing exceptional ethylbenzene recovery.