Multivariate Metal–Organic Frameworks Prepared by Simultaneous Metal/Ligand Exchange for Enhanced C2–C3 Selective Recovery from Natural Gas

Recovering light alkanes from natural gas is a critical but challenging process in petrochemical production. Herein, we propose a postmodification strategy via simultaneous metal/ligand exchange to prepare multivariate metal–organic frameworks with enhanced capacity and selectivity of ethane (C2H6) and propane (C3H8) for their recovery from natural gas with methane (CH4) as the primary component. By utilizing the Kuratowski-type secondary building unit of CFA-1 as a scaffold, namely, {Zn5(OAc)4}6+, the Zn2+ metal ions and OAc– ligands were simultaneously exchanged by other transition metal ions and halogen ligands under mild conditions. Inspiringly, this postmodification treatment can give rise to improved capacity for C2H6 and C3H8 without a noticeable increase in CH4 uptake, and consequently, it resulted in significantly enhanced selectivity toward C2H6/CH4 and C3H8/CH4. In particular, by adjusting the species and amount of the modulator, the optimal sample CFA-1-NiCl2-2.3 demonstrated the maximum capacities of C2H6 (5.00 mmol/g) and C3H8 (8.59 mmol/g), increased by 29 and 32% compared to that of CFA-1. Moreover, this compound exhibited excellent separation performance toward C2H6/CH4 and C3H8/CH4, with high uptake ratios of 6.9 and 11.9 at 298 K and 1 bar, respectively, superior to the performance of a majority of the reported MOFs. Molecular simulations were applied to unravel the improved separation mechanism of CFA-1-NiCl2-2.3 toward C2H6/CH4 and C3H8/CH4. Furthermore, remarkable thermal/chemical robustness, moderate isosteric heat, and fully reproducible breakthrough experiments were confirmed on CFA-1-NiCl2-2.3, indicating its great potential for light alkane recovery from natural gas.