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With the PTFE membrane as the substrate, a novel Ag-based catalytic membrane reactor (CMR) was fabricated by deep-permeation synthesis fabrication (DPSF). In DPSF, ZIF-8 was first assembled inside the membrane pores by permeation flow and the depositing reaction of Zn 2+ , and 2-methylimidazole solutions flow through the membrane synergistically. Then, Ag was reduced inside the pores impregnating ZIF-8 nanoclusters by Ag + and reductant solutions flowing through the membrane similarly. The TEM images of the cross-sectional membrane exhibited the composite nanoparticles of Ag+ZIF-8 with good dispersion and size distribution (10−50 nm). The as-synthesized (Ag+ZIF-8)@PTFE was applied to the catalytic reduction of p-nitroaniline to pphenylenediamine in a continuous flow-through reactor and presented remarkable catalyzing performance. The maximal apparent reaction rate constant is 3−4 orders of magnitude higher than that reported with good stability.

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A bimetallic catalytic membrane microreactor (CMMR) with bimetallic nanoparticles in membrane pores has been fabricated via flowing synthesis. The bimetallic nanoparticle is successfully immobilized in membrane pores along its thickness direction. Enhanced synergistic catalysis can be expected in this CMMR. As a concept-of-proof, Cu–Ag core–shell nanoparticles have been fabricated and immobilized in membrane pores for p-nitrophenol (p-NP) hydrogenation. Transmission electron microscopy (TEM) for the characterization of the bimetallic core–shell nanostructure and X-ray photoelectron spectroscopy (XPS) for the characterization of the electron transfer behavior between Cu–Ag bimetal have been performed. The Ag shell on the core of Cu can improve the utilization of Ag atoms, and electron transfer between bimetallic components can promote the formation of high electron density active sites as well as active hydrogen with strong reducing properties on the Ag surface. The dispersed membrane pore can prevent nanoparticle aggregation, and the contact between the reaction fluid and catalyst is enhanced. The enhanced mass transfer can be achieved by the plug-flow mode during the process of hydrogenation catalysis. The p-NP conversion rate being over 95% can be obtained under the condition of a membrane flux of 1.59 mL·cm–2·min–1. This Cu–Ag/PES CMMR has good stability and has a potential application in industry.

It is challenging to fabricate stable, complete, controllable, homogeneous metal–organic framework composites. Hereof, we suggested a versatile method where nanocrystals were assembled inside the porous polymer by synergistic chemical synthesis and permeation flow in and through its pores. The poly­(tetrafluoroethylene) (PTFE)/ZnO and PTFE/ZIF-8 were fabricated as the prototype of the composites. For fabricating the composite, ZnO was first synthesized inside the pores followed by ligand vapor treatment. The even and well-distributed ZnO nanorods of 10–30 nm were synthesized inside pores of PTFE and converted into ZIF-8. The ZnO and ZIF-8 were quantified in 281 and 431 mg g–1 against the original PTFE, respectively. The composite is stable and the nanocrystals are not readily washed away. The adsorption uptake (C3 > C2 > C1) of the light hydrocarbon gases for the PTFE/ZIF-8 nanocomposite were preliminarily evaluated. The adsorption selectivities were calculated, where the selectivities for C2H6/CH4 and C3H8/CH4 were 10.9 and 42.8, respectively.