Quasi-open Cu(I) sites for efficient CO separation with high O2/H2O tolerance.

Abstract

Carbon monoxide (CO) separation relies on chemical adsorption but suffers from the difficulty of desorption and instability of open metal sites against O2, H2O and so on. Here we demonstrate quasi-open metal sites with hidden or shielded coordination sites as a promising solution. Possessing the trigonal coordination geometry (sp2), Cu(I) ions in porous frameworks show weak physical adsorption for non-target guests. Rational regulation of framework flexibility enables geometry transformation to tetrahedral geometry (sp3), generating a fourth coordination site for the chemical adsorption of CO. Quantitative breakthrough experiments at ambient conditions show CO uptakes up to 4.1 mmol g-1 and CO selectivity up to 347 against CO2, CH4, O2, N2 and H2. The adsorbents can be completely regenerated at 333-373 K to recover CO with a purity of >99.99%, and the separation performances are stable in high-concentration O2 and H2O. Although CO leakage concentration generally follows the structural transition pressure, large amounts (>3 mmol g-1) of ultrahigh-purity (99.9999999%, 9N; CO concentration < 1 part per billion) gases can be produced in a single adsorption process, demonstrating the usefulness of this approach for separation applications.