TY - JOUR

T1 - Engineering of Covalent Organic Framework Nanosheet Membranes for Fast and Efficient Ion Sieving

T2 - Charge-Induced Cation Confined Transport

AU - Wang, Rui

AU - Ding, Li

AU - Xue, Jian

AU - Wu, Haoyu

AU - Cai, Chengzhi

AU - Qiao, Zhiwei

AU - Caro, Jürgen

AU - Wang, Haihui

N1 - Publisher Copyright: © 2024 Wiley-VCH GmbH.

PY - 2024/10/15

Y1 - 2024/10/15

N2 - Artificial membranes with ion-selective nanochannels for high-efficiency mono/divalent ion separation are of great significance in water desalination and lithium-ion extraction, but they remain a great challenge due to the slight physicochemical property differences of various ions. Here, the successful synthesis of two-dimensional TpEBr-based covalent organic framework (COF) nanosheets, and the stacking of them as consecutive membranes for efficient mono/divalent ion separation is reported. The obtained COF nanosheet membranes with intrinsic one-dimensional pores and abundant cationic sites display high permeation rates for monovalent cations (K+, Na+, Li+) of ≈0.1–0.3 mol m−2 h−1, while the value of divalent cations (Ca2+, Mg2+) is two orders of magnitude lower, resulting in an ultrahigh mono/divalent cation separation selectivity up to 130.4, superior to the state-of-the-art ion sieving membranes. Molecular dynamics simulations further confirm that electrostatic interaction controls the confined transport of cations through the cationic COF nanopores, where multivalent cations face i) strong electrostatic repulsion and ii) steric transport hindrance since the large hydrated divalent cations are retarded due to a layer of strongly adsorbed chloride ions at the pore wall, while smaller monovalent cations can swiftly permeate through the nanopores.

AB - Artificial membranes with ion-selective nanochannels for high-efficiency mono/divalent ion separation are of great significance in water desalination and lithium-ion extraction, but they remain a great challenge due to the slight physicochemical property differences of various ions. Here, the successful synthesis of two-dimensional TpEBr-based covalent organic framework (COF) nanosheets, and the stacking of them as consecutive membranes for efficient mono/divalent ion separation is reported. The obtained COF nanosheet membranes with intrinsic one-dimensional pores and abundant cationic sites display high permeation rates for monovalent cations (K+, Na+, Li+) of ≈0.1–0.3 mol m−2 h−1, while the value of divalent cations (Ca2+, Mg2+) is two orders of magnitude lower, resulting in an ultrahigh mono/divalent cation separation selectivity up to 130.4, superior to the state-of-the-art ion sieving membranes. Molecular dynamics simulations further confirm that electrostatic interaction controls the confined transport of cations through the cationic COF nanopores, where multivalent cations face i) strong electrostatic repulsion and ii) steric transport hindrance since the large hydrated divalent cations are retarded due to a layer of strongly adsorbed chloride ions at the pore wall, while smaller monovalent cations can swiftly permeate through the nanopores.

KW - cationic covalent organic frameworks (cationic COFs)

KW - confined transport

KW - ion sieving

KW - membrane separation

KW - nanosheets

UR - http://www.scopus.com/inward/record.url?scp=85206306713&partnerID=8YFLogxK

U2 - 10.1002/smtd.202401111

DO - 10.1002/smtd.202401111

M3 - Article

AN - SCOPUS:85206306713

JO - Small Methods

JF - Small Methods

ER -