Permeation Properties of Disordered Metal-Organic Framework Membranes Made by Vapor Phase Ligand Treatment
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The research approach will employ vapor-phase synthesis,testing,simulation,and characterization approaches in order to test hypotheses regarding the flexibility of nanoconfined ZIFs.This class of nanocomposite ZIF thin films is unique and exhibits interesting separations performance in part because of a unique synthesis approach:an all-vapor-phase ligand induced permselectivation(LIPS)method(Science 361,1008-1011(2018)),and a modification of LIPS through a vapor phase linker/ligand treatment(VPLT)method that leads to large selectivity improvements for certain gas mixtures(Angew.Chem.Int.Ed.58,16390–16394(2019)).In particular,the propylene/propane separation performance of LIPS/VPLT ZIF membranes confined(entirely or partially)inside mesopores is remarkably superior to that of most conventional ZIF membranes consisting of unconfined(deposited on the external surface of porous supports)polycrystalline films.However,a fundamental understanding of the factors that lead to such performance is not available.
It is hypothesized that the mesoporous support,which serves as the matrix of the selective ZIF component of the membrane,through interfacial interactions plays a vital role in affecting the ZIF structure.The combination of LIPS with VPLT is an essential part of a methodology for testing this hypothesis.This research consists of four interwoven methodological challenges:(i)extension of the LIPS/VPLT methods to create a range of membrane nanostructures;(ii)adsorption isotherm and diffusivity determination using a combination of experiments and mathematical analysis;(iii)structure determination;and(iv)molecular-level understanding using simulations.Task 1 will be performed at JHU(Tsapatsis)to address(i)and(ii)above,while Task 2 will encompass characterization methods(iii)and be accomplished at Brookhaven National Lab and SBU(Boscoboinik).Task 3 focusses on simulations(iv),and it will be performed at UMN(Siepmann).
Overall,this research elucidates structural characteristics that are responsible for the high performance of confined ZIF nanocomposites in order to extend the use of LIPS and VPLT to other confined metal organic framework(MOF)nanocomposites.
1.Zeolitic Imidazolate Framework Membranes: Novel Synthesis Methods and Progress Toward Industrial Use
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- membrane; distillation; metal-organic framework; separation;hydrocarbons; gas;METAL-ORGANIC FRAMEWORK; MOLECULAR-SIEVE MEMBRANE; HOLLOW-FIBERMEMBRANES; ROOM-TEMPERATURE SYNTHESIS; FREE ZIF-8 MEMBRANES;PROPYLENE/PROPANE SEPARATION; COMPOSITE MEMBRANES; THERMAL-STABILITY;GAS SEPARATIONS; RAPID SYNTHESIS
In the last decade, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes. In this review, we highlight unique structural properties of ZIFs that allow them to achieve certain important separations, like that of propylene from propane, and summarize the state of the art in ZIF thin-film deposition on porous substrates and their modification by postsynthesis treatments. We also review the reported membrane performance for representative membrane synthesis approaches and attempt to rank the synthesis methods with respect to potential for scalability. To compare the dependence of membrane performance on membrane synthesis methods and operating conditions, we map out fluxes and separation factors of selected ZIF-8 membranes for propylene/propane separation. Finally, we provide future directions considering the importance of further improvements in scalability, cost effectiveness, and stable performance under industrially relevant conditions.
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