Highly Efficient Separation of Intermediate‐Size m‐Xylene from Xylenes via a Length‐Matched Metal‐Organic Framework with Optimal Oxygen Sites Distribution

Abstract Xylene separation is crucial but challenging, especially for the preferential separation of the intermediate‐size m‐xylene from xylene mixtures. Herein, exploiting the differences in molecular length and alkyl distribution among xylenes, we present a length‐matched metal–organic framework, formulated as Al(OH)[O 2 C−C 4 H 2 O−CO 2 ], featuring an effective pore size corresponding to m‐xylene molecular length combined with multiple negative O hydrogen bond donors distribution, can serve as a molecular trap for efficient preferential separation of the intermediate‐size m‐xylene. Benchmark separation performance was achieved for separating m‐xylene from a ternary mixture of m‐xylene/o‐xylene/p‐xylene, with simultaneous record‐high m‐xylene uptake (1.3 mmol g −1 ) and m‐xylene/p‐xylene selectivity (5.3) in the liquid‐phase competitive adsorption. Both vapor‐ and liquid‐phase fixed‐bed tests confirmed its practical separation capability with benchmark dynamic m‐xylene/p‐xylene and m‐xylene/o‐xylene selectivities, as well as excellent regenerability. The selective and strong m‐xylene binding affinity among xylene molecules was further elucidated by simulations, validating the effectiveness of such a pore environment for the separation of intermediate‐size molecules.