Polar‐Nonpolar Synergistic Incorporation in Metal‐Organic Frameworks for Promoting Methane Separation From Natural Gas

ABSTRACT The separation of CH 4 from natural gas is an industrially significant yet challenging task. In this study, we rationally designed metal‐organic framework (MOF)‐based adsorbents with polar‐nonpolar synergistic sites to enhance the efficient separation of CH 4 from natural gas. Our study demonstrates that the adsorbents exhibit superior adsorption capacity for C 3 H 8 and C 2 H 6 compared to CH 4 , as well as high separation selectivity for C 3 H 8 /CH 4 (1336) and C 2 H 6 /CH 4 (46), effectively overcoming the trade‐off between adsorption capacity and selectivity. Breakthrough experiments further confirm the exceptional dynamic separation performance of the adsorbents for the C 3 H 8 /C 2 H 6 /CH 4 ternary mixture under various operating conditions, achieving >99.99% CH 4 purity and a yield of 11.27 mmol·g −1 . Molecular simulations and theoretical calculations elucidate that the incorporated polar and nonpolar sites in the adsorbents provide multiple strong interactions, which significantly enhance the separation of CH 4 from the C 3 H 8 /C 2 H 6 /CH 4 mixture.