Anionic Ni-Based Metal–Organic Framework with Li(I) Cations in the Pores for Efficient C₂H₂/CO₂ Separation

Acetylene (C 2 H 2 ) is widely used as a raw material for producing various downstream commodities in the petrochemical and electronic industry. Therefore, the acquisition of high-purity C 2 H 2 from a C 2 H 2 /CO 2 mixture produced by partial methane combustion or thermal hydrocarbon cracking is of great significance yet highly challenging due to their similar physical and chemical properties. Herein, we report an anionic metal–organic framework (MOF) named LIFM-210, which has Li + cations in the pores and shows a higher adsorption affinity for C 2 H 2 than CO 2 . LIFM-210 is constructed by a unique tetranuclear Ni(II) cluster acting as a 10-connected node and an organic ligand acting as a 5-connected node. Single-component adsorption and transient breakthrough experiments demonstrate the good C 2 H 2 selective separation performance of LIFM-210. Theoretical calculations revealed that Li + ions strongly prefer C 2 H 2 to CO 2 and are primary adsorption sites, playing vital roles in the selective separation of C 2 H 2 /CO 2 .