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A modification in the gas separation performance of zeolitic imidazolate framework (ZIF)-supported hollow fiber (HF) membranes by means of an imine-condensation functionalization reaction carried out by microfluidics is reported. The accommodation of voluminous amine molecules in the SIM-1, Zn(4-methyl-5-imidazolecarboxaldehyde)2, also known as ZIF-94, sod structure during the functionalization reaction caused the ZIF atoms to be rearranged in a less dense rho structure, with a wider pore diameter and a diminished CO2 affinity. These changes had effects on the membrane performance, resulting in an enhanced CO2 permeance while maintaining a good permeance–selectivity balance. ZIF aldehyde-containing SIM-1 membranes were earlier prepared on the inner side of polymeric P84® HF using a microfluidic approach. The SIM-1 membranes displayed very interesting results in the separation of gas mixtures of great relevance to the natural gas field. High selectivities in the separation of He/CH4 (160), H2/CH4 (136) and CO2/CH4 (38) mixtures were achieved, and these are the first SIM-1 membranes with such a high separation performance to the best of our knowledge. These SIM-1 membranes were in situ stepwise functionalized with long-chain amine solutions, namely, hexyl- and nonylamine. Microfluidics allowed the easy sequential implementation of this post-reaction step in the membrane fabrication procedure. An imine-condensation reaction took place between the aldehyde groups in the 4-methyl-5-imidazolecarboxaldehyde ligand forming SIM-1 and the corresponding amines. The extent of the reaction was analyzed by FTIR, TGA and XRD, together with the changes in the textural properties and the adsorption capacities. [ABSTRACT FROM AUTHOR]

The field of metal–organic framework based mixed matrix membranes (M4s) is critically reviewed, with special emphasis on their application in CO2 capture during energy generation. After introducing the most relevant parameters affecting membrane performance, we define targets in terms of selectivity and productivity based on existing literature on process design for pre- and post-combustion CO2 capture. Subsequently, the state of the art in M4s is reviewed against these targets. Because final application of these membranes will only be possible if thin separation layers can be produced, the latest advances in the manufacture of M4 hollow fibers are discussed. Finally, the recent efforts in understanding the separation performance of these complex composite materials and future research directions are outlined. [ABSTRACT FROM AUTHOR]

Zeolitic imidazolate framework-93 (ZIF-93) continuous membranes were synthesized on the inner side of P84 co-polyimide hollow fiber supports by microfluidics. MOFs and polymers showed high compatibility and the membrane exhibited H2–CH4 and CO2–CH4 separation selectivities of 97 (100 °C) and 17 (35 °C), respectively. [ABSTRACT FROM AUTHOR]