Efficient One-Step Purification of C₁and C₂Hydrocarbons over CO₂in a New CO₂-Selective MOF with a Gate-Opening Effect

Removing CO2 impurity is an essential industrial process in the purification of hydrocarbons. The most promising strategy is the one-step collection of high-purity hydrocarbons by employing CO2-selective adsorbents, which requires improving the CO2 adsorption and separation behavior of adsorbents, especially the low-pressure performance under actual industrial conditions. Herein, we constructed a new flexible metal–organic framework [Zn(odip)0.5(bpe)0.5(CH3OH)]·0.5NMF·H2O (1) (H4odip = 5,5′-oxydiisophthalic acid, bpe = 1,2-bi(4-pyridyl)ethylene, and NMF = N-methylformamide) containing rich ether O adsorption sites in the channels that exhibits remarkable adsorption capacity for CO2 (118.7 cm3 g–1) due to the only gate-opening-type abrupt adsorption of CO2 at room temperature. Its low affinity for other competing gases enables it to deliver high selectivity for the adsorption of CO2 over C1 and C2 hydrocarbons. For equimolar mixtures of CO2–CH4 and CO2–C2H2, the selectivities are 376.0 and 13.2, respectively. Molecular simulations disclose more abundant adsorption sites for CO2 than hydrocarbons in 1. The breakthrough separation performances combined with remarkable stability and recyclability further verify that 1 is a promising adsorbent that can efficiently extract high-purity hydrocarbons through selective capture of CO2.