Quasi-open Cu( i ) sites for efficient CO separation with high O 2 /H 2 O tolerance

Carbon monoxide (CO) separation relies on chemical adsorption but suffers from the difficulty of desorption and instability of open metal sites against O 2 , H 2 O 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 ( sp 2 ), 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 ( sp 3 ), 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 CO 2 , CH 4 , O 2 , N 2 and H 2 . 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 O 2 and H 2 O. 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.