Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports

Handle URI:
http://hdl.handle.net/10754/625042
Title:
Synthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supports
Authors:
Barankova, Eva ( 0000-0003-0683-1545 )
Abstract:
Since the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good chemical and thermal stability, recent commercial availability and attractive pore size. The aim of this work is to develop convenient methods for growing ZIF thin layers on polymer supports to obtain defect-free ZIF membranes with good gas separation properties. We present new approaches for ZIF membranes preparation on polymers. We introduce zinc oxide nanoparticles in the support as a secondary metal source for ZIF-8 growth. Initially the ZnO particles were incorporated into the polymer matrix and later on the surface of the polymer by magnetron sputtering. In both cases, the ZnO facilitated to create more nucleation opportunities and improved the ZIF-8 growth compared to the synthesis without using ZnO. By employing the secondary seeded growth method, we were able to obtain thin (900 nm) ZIF-8 layer with good gas separation performance. Next, we propose a metal-chelating polymer as a suitable support for growing ZIF layers. Defect-free ZIF-8 films with a thickness of 600 nm could be obtained by a contra-diffusion method. ZIF-8 membranes were tested for permeation of hydrogen and hydrocarbons, and one of the highest selectivities reported so far for hydrogen/propane, and propylene/propane was obtained. Another promising method to facilitate the growth of MOFs on polymeric supports is the chemical functionalization of the support surface with functional groups, which can complex metal ions and which can covalently bond the MOF crystals. We functionalized the surface of a common porous polymeric membrane with amine groups, which took part in the reaction to form ZIF-8 nanocrystals. We observed an enhancement in adhesion between the ZIF layer and the support. The effect of parameters of the contra-diffusion experiment (such as temperature lower than room temperature and synthesis times shorter than 1 hour) on ZIF-8 membrane properties was evaluated. We could prepare one of the thinnest (around 200 nm) yet selective ZIF-8 films reported.
Advisors:
Peinemann, Klaus-Viktor ( 0000-0003-0309-9598 )
Committee Member:
Lai, Zhiping ( 0000-0001-9555-6009 ) ; Han, Yu ( 0000-0003-1462-1118 ) ; Vankelecom, Ivo
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Program:
Chemical and Biological Engineering
Issue Date:
Jun-2017
Type:
Dissertation
Appears in Collections:
Dissertations

Full metadata record

DC FieldValue Language
dc.contributor.advisorPeinemann, Klaus-Viktoren
dc.contributor.authorBarankova, Evaen
dc.date.accessioned2017-06-15T13:27:25Z-
dc.date.available2017-06-15T13:27:25Z-
dc.date.issued2017-06-
dc.identifier.urihttp://hdl.handle.net/10754/625042-
dc.description.abstractSince the discovery of size-selective metal-organic frameworks (MOF) researchers have tried to manufacture them into gas separation membranes. ZIF-8 became the most studied MOF for membrane applications mainly because of its simple synthesis, good chemical and thermal stability, recent commercial availability and attractive pore size. The aim of this work is to develop convenient methods for growing ZIF thin layers on polymer supports to obtain defect-free ZIF membranes with good gas separation properties. We present new approaches for ZIF membranes preparation on polymers. We introduce zinc oxide nanoparticles in the support as a secondary metal source for ZIF-8 growth. Initially the ZnO particles were incorporated into the polymer matrix and later on the surface of the polymer by magnetron sputtering. In both cases, the ZnO facilitated to create more nucleation opportunities and improved the ZIF-8 growth compared to the synthesis without using ZnO. By employing the secondary seeded growth method, we were able to obtain thin (900 nm) ZIF-8 layer with good gas separation performance. Next, we propose a metal-chelating polymer as a suitable support for growing ZIF layers. Defect-free ZIF-8 films with a thickness of 600 nm could be obtained by a contra-diffusion method. ZIF-8 membranes were tested for permeation of hydrogen and hydrocarbons, and one of the highest selectivities reported so far for hydrogen/propane, and propylene/propane was obtained. Another promising method to facilitate the growth of MOFs on polymeric supports is the chemical functionalization of the support surface with functional groups, which can complex metal ions and which can covalently bond the MOF crystals. We functionalized the surface of a common porous polymeric membrane with amine groups, which took part in the reaction to form ZIF-8 nanocrystals. We observed an enhancement in adhesion between the ZIF layer and the support. The effect of parameters of the contra-diffusion experiment (such as temperature lower than room temperature and synthesis times shorter than 1 hour) on ZIF-8 membrane properties was evaluated. We could prepare one of the thinnest (around 200 nm) yet selective ZIF-8 films reported.en
dc.language.isoenen
dc.subjectMetal organic frameworken
dc.subjectMOF membraneen
dc.subjectMOF Polymer Membraneen
dc.subjectZIF-8en
dc.subjectGas separationen
dc.subjectThin film composite membraneen
dc.titleSynthesis of Thin Film Composite Metal-Organic Frameworks Membranes on Polymer Supportsen
dc.typeDissertationen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
thesis.degree.grantorKing Abdullah University of Science and Technologyen_GB
dc.contributor.committeememberLai, Zhipingen
dc.contributor.committeememberHan, Yuen
dc.contributor.committeememberVankelecom, Ivoen
thesis.degree.disciplineChemical and Biological Engineeringen
thesis.degree.nameDoctor of Philosophyen
dc.person.id124193en
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