Optimizing Trace Acetylene Removal from Acetylene/Ethylene Mixture in a Flexible Metal-Organic Framework by Crystal...

Improving the gas separation performance of metal-organic frameworks (MOFs) by crystal downsizing is an important but often overlooked issue. Here, we report three different-sized flexible ZUL-520 MOFs (according to the crystal size from large to small, the three samples are, respectively, named ZUL-520-0, ZUL-520-1, and ZUL-520-2) with the same chemical structure for optimizing trace acetylene (C₂H₂) removal from acetylene/ethylene (C₂H₂/C₂H₄) mixture. The three differently sized activated ZUL-520 (denoted as ZUL-520a) exhibited almost identical C₂H₂ uptake of 4.8 mmol/g at 100 kPa, while the C₂H₂ uptake at 1 kPa increased with a downsizing crystal. The C₂H₂ uptake of activated ZUL-520-2 (denoted as ZUL-520-2a) at 1 kPa was ∼55% higher than that of activated ZUL-520-0 (denoted as ZUL-520-0a). The adsorption isotherms and adsorption kinetics validated that gas adsorptive separation is governed not only by adsorption thermodynamics but also by adsorption kinetics. In addition, all three different-sized ZUL-520a MOFs showed high C₂H₂/C₂H₄ selectivity. Grand canonical Monte Carlo (GCMC) simulations and dispersion-corrected density functional theory (DFT-D) computations illustrated a plausible mechanism of C₂H₂ adsorption in MOFs. Importantly, breakthrough experiments demonstrated that ZUL-520a can effectively separate the C₂H₂/C₂H₄ (1/99, v/v) mixture and the C₂H₄ productivity obtained by ZUL-520-2a was much higher than that by ZUL-520-0a. Our work may provide an easy but powerful strategy for upgrading the performance of gas adsorptive separation in MOFs.