Benchmark C2 H2 /CO2 Separation in an Ultra-Microporous Metal-Organic Framework via Copper(I)-Alkynyl Chemistry

Abstract

Separation of acetylene from carbon dioxide remains a daunting challenge because of their very similar molecular sizes and physical properties. We herein report the first example of using copper(I)-alkynyl chemistry within an ultra-microporous MOF (Cu^I @UiO-66-(COOH)₂ ) to achieve ultrahigh C₂ H₂ /CO₂ separation selectivity. The anchored Cu^I ions on the pore surfaces can specifically and strongly interact with C₂ H₂ molecule through copper(I)-alkynyl π-complexation and thus rapidly adsorb large amount of C₂ H₂ at low-pressure region, while effectively reduce CO₂ uptake due to the small pore sizes. This material thus exhibits the record high C₂ H₂ /CO₂ selectivity of 185 at ambient conditions, significantly higher than the previous benchmark ZJU-74a (36.5) and ATC-Cu (53.6). Theoretical calculations reveal that the unique π-complexation between Cu^I and C₂ H₂ mainly contributes to the ultra-strong C₂ H₂ binding affinity and record selectivity. The exceptional separation performance was evidenced by breakthrough experiments for C₂ H₂ /CO₂ gas mixtures. This work suggests a new perspective to functionalizing MOFs with copper(I)-alkynyl chemistry for highly selective separation of C₂ H₂ over CO₂ .

Keywords: acetylene capture; copper(I)-alkynyl chemistry; gas separation; porous material; π-complexation.