Donnan Effect-Engineered Covalent Organic Framework Membranes toward Size- and Charge-Based Precise Molecular Sieving

Covalent organic frameworks (COFs), with ordered pores and well-defined topology, are ideal materials for nanofiltration (NF) membranes because of their capacity of transcending the permeance/selectivity trade-off predicament. However, most reported COF-based membranes are focused on separating molecules with different sizes, resulting in low selectivity to similar molecules with different charges. Here, the negatively charged COF layer was fabricated in situ on a microporous support for the separation of molecules with different sizes and charges. Ultrahigh water permeance (216.56 L m^-2 h^-1 bar^-1) was obtained because of the ordered pores and excellent hydrophilicity, which exceeds that of most membranes with similar rejections. For the first time, we used multifarious dyes with different sizes and charges, for the investigation of the selectivity behavior caused by the Donnan effect and size exclusion. The obtained membranes represent superior rejections to negatively and neutrally charged dyes larger than 1.3 nm, while positively charged dyes with a size of 1.6 nm can pass through the membrane, resulting in the separation of negative/positive mixed dyes with similar molecular sizes. This strategy of combining the Donnan effect and size exclusion in nanoporous materials may evolve into a generic platform for sophisticated separation.