Membrane technology has attracted great industrial interest in carbon capture and separation owing to the merits of energy-efficiency, environmental friendliness and low capital investment. Conventional polymeric membranes for CO₂ separation suffer from the trade-off between permeability and selectivity. Introducing porous fillers in polymers is one approach to enhance membrane separation performance. Metal-organic frameworks (MOFs), with ordered porous structure and diverse chemical functionalities, are promising fillers to prepare mixed matrix membranes (MMMs) for CO₂ separation. However, the main issue of MOF based MMMs in industry is their stability and processability. This review analyses recent work on stable and scalable MOF based MMMs for CO₂ separation. The typical stable MOFs, MOF-based MMMs and the scalable MOF synthesis are summarized. A large number of MOF-based MMM suffer from instability upon exposure to contaminants. For that reason, we also discuss the use of covalent organic frameworks (COFs) as an alternative to prepare MMMs for CO₂ separation, considering their excellent stability and good compatibility with polymers. Finally, a brief conclusion and current challenges on obtaining scalable and stable MMMs are outlined. This review may provide some guidance for designing high performance MMMs for industrial CO₂ capture and separation to help achieving carbon neutrality.

Highly selective thin-film composite membranes for hot hydrogen sieving are prepared via the pyrolysis of thin cyclomatric polyphenoxy phosphazene films that are prepared via a non-conventional interfacial polymerization of hexachlorocyclotriphosphazene with 1,3,5-trihydroxybenzene or m-dihydroxybenzene. The presence of the cyclic phosphazene ring within the weakly branched polymer films gives rise to a distinct thermal degradation evolution, with an onset temperature of around 200 °C. For the trihydroxybenzene derived material, the hydrogen permselectivity of the films shows a maximum pyrolysis temperature of around 450 °C. At this temperature a compact atomic structure is obtained that comprises mostly disordered carbon and accommodates P–O–C and P–O–P bonds. During thermal treatment, these films reveal molecular sieving with permselectivities exceeding 100 for H₂/N₂, H₂/CH₄, and H₂/CO₂, and a hydrogen permeance of 2 × 10⁻¹⁰ to 1.5 × 10⁻⁸ mol/m²/s/Pa (0.6-44.8GPU), at 200 °C. At ambient temperatures, thin films are very effective barriers for small gas molecules. Because of the inexpensive facile synthesis and low- temperature pyrolysis, the polyphosphazene films have the potential for use in high-temperature industrial gas separations, as well as for use as barriers such as liners in high- pressure hydrogen storage vessels at ambient temperature.

A series of cyclomatrix polyphosphazene films have been prepared by nonaqueous interfacial polymerization (IP) of small aromatic hydroxyl compounds in a potassium hydroxide dimethylsulfoxide solution and hexachlorocyclotriphosphazene in cyclohexane on top of ceramic supports. Via the amount of dissolved potassium hydroxide, the extent of deprotonation of the aromatic hydroxyl compounds can be changed, in turn affecting the molecular structure and permselective properties of the thin polymer networks ranging from hydrogen/oxygen barriers to membranes with persisting hydrogen permselectivities at high temperatures. Barrier films are obtained with a high potassium hydroxide concentration, revealing permeabilities as low as 9.4 × 10^-17 cm³ cm cm^-2 s^-1 Pa^-1 for hydrogen and 1.1 × 10^-16 cm³ cm cm^-2 s^-1 Pa^-1 for oxygen. For films obtained with a lower concentration of potassium hydroxide, single gas permeation experiments reveal a molecular sieving behavior, with a hydrogen permeance of around 10^-8 mol m^-2 s^-1 Pa^-1 and permselectivities of H₂/N₂ (52.8), H₂/CH₄ (100), and H₂/CO₂ (10.1) at 200 °C.

An interfacial polymerization process is introduced for the fabrication of thermally stable cyclomatrix poly(phenoxy)phosphazenes thin-film composite membranes that can sieve hydrogen from hot gas mixtures. By replacing the conventionally used aqueous phase with dimethyl sulfoxide/potassium hydroxide, a variety of biphenol molecules are deprotonated to aryloxide anions that react with hexachlorocyclotriphosphazene dissolved in cyclohexane to form a thin film of a highly cross-linked polymer film. The film membranes have persistent permselectivities for hydrogen over nitrogen (16–27) and methane (14–30) while maintaining hydrogen permeances in the order of (10⁻⁸–10⁻⁷ mol m⁻²s⁻¹Pa⁻¹) at temperatures as high as 260 °C and do not lose their performance after exposure to 450 °C. The unprecedented thermal stability of these polymer membranes opens the potential for industrial membrane gas separations at elevated temperatures.