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

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 (C 2 H 2 ) removal from acetylene/ethylene (C 2 H 2 /C 2 H 4 ) mixture. The three differently sized activated ZUL-520 (denoted as ZUL-520a) exhibited almost identical C 2 H 2 uptake of 4.8 mmol/g at 100 kPa, while the C 2 H 2 uptake at 1 kPa increased with a downsizing crystal. The C 2 H 2 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 C 2 H 2 /C 2 H 4 selectivity. Grand canonical Monte Carlo (GCMC) simulations and dispersion-corrected density functional theory (DFT-D) computations illustrated a plausible mechanism of C 2 H 2 adsorption in MOFs. Importantly, breakthrough experiments demonstrated that ZUL-520a can effectively separate the C 2 H 2 /C 2 H 4 (1/99, v/v) mixture and the C 2 H 4 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.