Covalent organic framework membranes for efficient separation of monovalent cations

Hongjian Wang; Yeming Zhai; Yang Li; Yu Cao; Benbing Shi; Runlai Li; Zingting Zhu; Haifei Jiang; Zheyuan Guo; Meidi Wang; Long Chen; Yawei Liu; Kai-Ge Zhou; Fusheng Pan; Zhongyi Jiang

doi:10.1038/s41467-022-34849-7

Covalent organic framework membranes for efficient separation of monovalent cations

Nat Commun. 2022 Nov 19;13(1):7123. doi: 10.1038/s41467-022-34849-7.

Authors

Hongjian Wang^{1

2}, Yeming Zhai^{3

4}, Yang Li⁵, Yu Cao^{1

2}, Benbing Shi^{1

2}, Runlai Li⁶, Zingting Zhu^{1

2}, Haifei Jiang^{1

2}, Zheyuan Guo^{1

2}, Meidi Wang^{1

2}, Long Chen⁷, Yawei Liu⁸, Kai-Ge Zhou^{3

4}, Fusheng Pan^{9

10

11

12

13}, Zhongyi Jiang^{14

15

16

17

18}

Affiliations

¹ Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, 300072, Tianjin, China.
² Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), 300072, Tianjin, China.
³ Institute of Molecular Plus, Department of Chemistry, Tianjin University, 300110, Tianjin, China.
⁴ Haihe Laboratory of Sustainable Chemical Transformations, 300192, Tianjin, China.
⁵ Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, 300072, Tianjin, China.
⁶ Department of Chemistry, National University of Singapore, Singapore, 117549, Singapore.
⁷ State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China.
⁸ Beijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, 100190, Beijing, China.
⁹ Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, 300072, Tianjin, China. fspan@tju.edu.cn.
¹⁰ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), 300072, Tianjin, China. fspan@tju.edu.cn.
¹¹ Haihe Laboratory of Sustainable Chemical Transformations, 300192, Tianjin, China. fspan@tju.edu.cn.
¹² Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, 350207, Fuzhou, China. fspan@tju.edu.cn.
¹³ Zhejiang Institute of Tianjin University, 315201, Ningbo, Zhejiang, China. fspan@tju.edu.cn.
¹⁴ Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, 300072, Tianjin, China. zhyjiang@tju.edu.cn.
¹⁵ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), 300072, Tianjin, China. zhyjiang@tju.edu.cn.
¹⁶ Haihe Laboratory of Sustainable Chemical Transformations, 300192, Tianjin, China. zhyjiang@tju.edu.cn.
¹⁷ Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, 350207, Fuzhou, China. zhyjiang@tju.edu.cn.
¹⁸ Zhejiang Institute of Tianjin University, 315201, Ningbo, Zhejiang, China. zhyjiang@tju.edu.cn.

Abstract

Covalent organic frameworks (COF), with rigid, highly ordered and tunable structures, can actively manipulate the synergy of entropic selectivity and enthalpic selectivity, holding great potential as next-generation membrane materials for ion separations. Here, we demonstrated the efficient separation of monovalent cations by COF membrane. The channels of COF membrane are decorated with three different kinds of acid groups. A concept of confined cascade separation was proposed to elucidate the separation process. The channels of COF membrane comprised two kinds of domains, acid-domains and acid-free-domains. The acid-domains serve as confined stages, rendering high selectivity, while the acid-free-domains preserve the pristine channel size, rendering high permeation flux. A set of descriptors of stage properties were designed to elucidate their effect on selective ion transport behavior. The resulting COF membrane acquired high ion separation performances, with an actual selectivity of 4.2-4.7 for K⁺/Li⁺ binary mixtures and an ideal selectivity of ~13.7 for K⁺/Li⁺.

Grants and funding

21838008/National Natural Science Foundation of China (National Science Foundation of China)