Highly Anion-Conductive Viologen-Based Two-Dimensional Polymer Membranes as Nanopower Generators.
Angew Chem Int Ed Engl
; : e202409349, 2024 Jul 04.
Article
em En
| MEDLINE
| ID: mdl-38962957
ABSTRACT
Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks (2D COFs) membranes hold great potential for harvesting sustainable osmotic energy. The nascent research has yet to simultaneously achieve high ionic flux and selectivity, primarily due to inefficient ion transport dynamics. This is directly related to ultrasmall pore size (<3â
nm), much smaller than the duple Debye length in the diluted electrolyte (6-20â
nm), as well as low charge density (<4.5â
mC m-2). Here, we introduce a π-conjugated viologen-based 2DP (V2DP) membrane possessing a large pore size of 4.5â
nm, strategically enhancing the overlapping of the electric double layer, coupled with an exceptional positive surface charge density (~6â
mC m-2). These characteristics enable the membrane to facilitate high anion flux while maintaining ideal selectivity. Notably, V2DP membranes realize an impressive current density of 5.5×103â
A m-2, surpassing benchmarks set by previously reported nanofluidic membranes. In the practical application scenario involving the mixing of artificial seawater and river water, the V2DP membranes exhibit a considerable ion transference number of 0.70 towards Cl-, contributing to an outstanding power density of ~55â
W m-2. Theoretical calculations reveal the important role of the large quantity of anion transport sites, which act as binding sites evenly located in the positively charged N-containing pyridine rings. These binding sites enable kinematic coupling and decoupling between anions and the V2DP skeleton, establishing a continuous Cl- ion transport pathway. This work demonstrates the great promise of large-area ultrathin 2DP membranes featuring highly organized charged ion transport networks when applied for osmotic energy conversion.
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MEDLINE
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En
Ano de publicação:
2024
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Article