Computational Guided Structural Design for Optimized Pore Size and Shape Metal‐Organic Framework Enabling One‐Step CH ₄ and C ₃ H

ABSTRACT

Current natural gas upgrading strategies primarily focus on CH ₄ recovery, treating C ₂ H ₆ and C ₃ H ₈ merely as impurities, which results in resource wastage. In this work, an advanced industrial operation, simultaneous separation of both pure CH ₄ and C ₃ H ₈ from CH ₄ /C ₂ H ₆ /C ₃ H ₈ ternary gas mixture was realized. Herein, based on semi‐empirical computational screening, the desired pore features were identified as an ideal nonpolar aromatic surface, a cage‐like geometry, and a suitable pore size. A new material Ni‐pza‐ina was directionally designed and synthesized. Sorption and separation experiments demonstrated that Ni‐pza‐ina served the industrial operation well with superior separation performance compared to its parent analogue Ni‐bdc‐ina and many other materials. Molecular simulations elucidated that the shape/size matching and distinct affinity differences between C ₂ H ₆ and C ₃ H ₈ are the governing factors, which are responsible for the successful separation of CH ₄ (6.05 mmol g ⁻¹ , purity > 99.5%) and C ₃ H ₈ (0.90 mmol g ⁻¹ , purity > 99.5%) from CH ₄ /C ₂ H ₆ /C ₃ H ₈ 85:10:5 (v/v/v) ternary in the breakthrough experiment. Finally, the industrial viability of Ni‐pza‐ina was demonstrated through an industrial two‐bed PSA process simulation, which achieved high recoveries of CH ₄ (69.17%) and C ₃ H ₈ (92.69%) in a single cycle, underscoring its promise for realistic industrial application.