In situ generated 2,5-pyrazinedicarboxylate and oxalate ligands leading to a Eu-MOF for selective capture of C2H2 from C2H2/CO2

Abstract

The separation of C₂H₂/CO₂ mixtures is a very important but highly challenging task due to their comparable physical natures and relative sizes. Herein, we report a europium-based 3D microporous MOF with a 4-connected two-nodal net with {4·5³·6²}₂{4²·6²·8²} topology, {[Eu₂(pzdc)(ox)₂(H₂O)₄]·5H₂O}_n (1) (H₂pzdc = 2,5-pyrazinedicarboxylic acid, H₂ox = oxalic acid), prepared by a hydrothermal method involving in situ generation of 2,5-pyrazinedicarboxylate and oxalate ligands. Two different temperatures were utilized to create two porous materials (1a and 1b) with channels of 4.8 × 5.4 Å and 4.1 × 6.3 Å, and 4.8 × 5.4 and 4.6 × 8.7 Ų, respectively. 1b shows a superior ability to selectively capture C₂H₂ from C₂H₂/CO₂ as compared with 1a. At 1 bar and 298 K, 1b takes up 4.10 mmol g⁻¹ C₂H₂ and 1.84 mmol g⁻¹ CO₂, respectively. In addition, at 298 K and 1 bar, 1b has a high selectivity for C₂H₂ over CO₂, with an IAST selectivity of 12.7 while the value for 1a is 3.2. The separation of C₂H₂/CO₂ with 1b also exhibits good reusability.