This review summarizes the major advances since 2012 in highly permeable and CO₂-selective polymer-based membrane materials.

Covalent organic frameworks (COFs) hold great promise in molecular separations owing to their robust, ordered and tunable porous network structures. Currently, the pore size of COFs is usually much larger than most small molecules. Meanwhile, the weak interlamellar interaction between COF nanosheets impedes the preparation of defect-free membranes. Herein, we report a series of COF membranes through a mixed-dimensional assembly of 2D COF nanosheets and 1D cellulose nanofibers (CNFs). The pore size of 0.45–1.0 nm is acquired from the sheltering effect of CNFs, rendering membranes precise molecular sieving ability, besides the multiple interactions between COFs and CNFs elevate membrane stability. Accordingly, the membranes exhibit a flux of 8.53 kg m⁻²h⁻¹with a separation factor of 3876 for n-butanol dehydration, and high permeance of 42.8 L m⁻²h⁻¹bar⁻¹with a rejection of 96.8% for Na₂SO₄removal. Our mixed-dimensional design may inspire the fabrication and application of COF membranes.

Molecular separations that enable selective transport of target molecules from gas and liquid molecular mixtures, such as CO₂ capture, olefin/paraffin separations, and organic solvent nanofiltration, represent the most energy sensitive and significant demands. Membranes are favored for molecular separations owing to the advantages of energy efficiency, simplicity, scalability, and small environmental footprint. A number of emerging microporous organic materials have displayed great potential as building blocks of molecular separation membranes, which not only integrate the rigid, engineered pore structures and desirable stability of inorganic molecular sieve membranes, but also exhibit a high degree of freedom to create chemically rich combinations/sequences. To gain a deep insight into the intrinsic connections and characteristics of these microporous organic material-based membranes, in this review, for the first time, we propose the concept of organic molecular sieve membranes (OMSMs) with a focus on the precise construction of membrane structures and efficient intensification of membrane processes. The platform chemistries, designing principles, and assembly methods for the precise construction of OMSMs are elaborated. Conventional mass transport mechanisms are analyzed based on the interactions between OMSMs and penetrate(s). Particularly, the ‘STEM’ guidelines of OMSMs are highlighted to guide the precise construction of OMSM structures and efficient intensification of OMSM processes. Emerging mass transport mechanisms are elucidated inspired by the phenomena and principles of the mass transport processes in the biological realm. The representative applications of OMSMs in gas and liquid molecular mixture separations are highlighted. The major challenges and brief perspectives for the fundamental science and practical applications of OMSMs are tentatively identified.

This review highlights the construction and regulation of two-dimensional nanochannel membranes (2DNCMs) as well as their applications in molecular and ionic separations.