Premium
Benchmark C 2 H 2 /CO 2 Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry
Author(s) -
Zhang Ling,
Jiang Ke,
Yang Lifeng,
Li Libo,
Hu Enlai,
Yang Ling,
Shao Kai,
Xing Huabin,
Cui Yuanjing,
Yang Yu,
Li Bin,
Chen Banglin,
Qian Guodong
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202102810
Subject(s) - microporous material , selectivity , copper , chemistry , acetylene , metal organic framework , gas separation , adsorption , molecule , metal , inorganic chemistry , organic chemistry , catalysis , membrane , biochemistry
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 C 2 H 2 /CO 2 separation selectivity. The anchored Cu I ions on the pore surfaces can specifically and strongly interact with C 2 H 2 molecule through copper(I)‐alkynyl π‐complexation and thus rapidly adsorb large amount of C 2 H 2 at low‐pressure region, while effectively reduce CO 2 uptake due to the small pore sizes. This material thus exhibits the record high C 2 H 2 /CO 2 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 C 2 H 2 mainly contributes to the ultra‐strong C 2 H 2 binding affinity and record selectivity. The exceptional separation performance was evidenced by breakthrough experiments for C 2 H 2 /CO 2 gas mixtures. This work suggests a new perspective to functionalizing MOFs with copper(I)‐alkynyl chemistry for highly selective separation of C 2 H 2 over CO 2 .