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Preparation of Functional Microporous Organic Polymers and Their Applications for Heterogeneous Catalysis and Dye Adsorption
기능성 마이크로기공성 유기고분자의 합성과 이의 불균질 촉매반응과 염료 흡착에의 활용

DC Field Value Language
dc.contributor.advisor장지영-
dc.contributor.author김종길-
dc.date.accessioned2017-10-27T16:39:36Z-
dc.date.available2017-10-27T16:39:36Z-
dc.date.issued2017-08-
dc.identifier.other000000144954-
dc.identifier.urihttps://hdl.handle.net/10371/136776-
dc.description학위논문 (박사)-- 서울대학교 대학원 공과대학 재료공학부, 2017. 8. 장지영.-
dc.description.abstractMicroporous organic polymers (MOPs) have many remarkable properties such as high surface area, low density, microporosity, and physicochemical stability. Various functional groups can be introduced to MOPs by the selection of reactants and post-modification, which facilitates practical uses of MOPs in various fields. However, most MOPs are obtained by insoluble powders because of their highly crosslinked structures, which causes poor processability of MOPs. In this study, various functional MOPs having shape-controlled structures were prepared and used for heterogeneous catalysis and dye adsorption.
Firstly, a MOP sponge was prepared using a homogenized electrospun nanofiber as the reinforcement. The Sonogashira-Hagihara coupling reaction of 2,5-dibromoaniline and 1,3,5-triethynylbenzene in a dispersion of homogenized electrospun nanofibers (PVASi) produced the compressible MOP composite with a core-shell structure (PVASi@TEDB-NH2). The polymer was uniformly grown on the surface of the nanofibers because TEDB-NH2 had primary amino groups that could form hydrogen bonds with the hydroxyl groups on the surface of PVASi. PVASi@TEDB-NH2 showed an average density and a BET surface area of 30.4 mg cm-3 and 447 m2g-1, respectively. The composite sponge was used for the removal of an organic dye dissolved in water. When PVASi@TEDB-NH2 was manually compressed and released in an aqueous methylene blue (MB) solution, the dye adsorption occurred rapidly.
Secondly, a microporous catalytic membrane based on a hypercrosslinked polymer (HCP) was prepared. A HCP-based nanofibrous membrane was synthesized via Friedel-Crafts reaction of 1,1-bi-2-naphthol in the presence of an aminated polyacrylonitrile (APAN) nanofibrous membrane as a substrate. The HCP was uniformly grown on the surface of the APAN nanofiber, which conferred a hierarchical porosity to the membrane. The HCP-based nanofibrous membrane showed a good mechanical strength and microporosity with a Brunaure-Emmett-Teller (BET) surface area of 375 m2 g-1. The HCP-based nanofibrous catalytic membrane (APAN-HCP-Pd) was prepared via the in-situ growth of palladium nanoparticles inside the membrane. The application of APAN-HCP-Pd as a catalytic membrane was investigated for the reduction of 4-nitrophenol.
Thirdly, a compressible monolithic catalyst based on a MOP nanotube sponge was prepared. The monolithic MOP sponge was synthesized via Sonogashira-Hagihara coupling reaction between 1,4-diiodotetrafluorobenzene and 1,3,5-triethynylbenzene in a co-solvent of toluene and TEA (2:1, v/v) without stirring. The MOP sponge had an intriguing microstructure, where tubular polymer fibers having a diameter of hundreds of nanometers were entangled. It showed hierarchical porosity with a Brunauer-Emmett-Teller (BET) surface area of 512 m2 g-1. The MOP sponge was functionalized with sulfur groups by the thiol-yne reaction. The functionalized MOP sponge exhibited a higher BET surface area than the MOP sponge by 13 % due to the increase in the total pore and micropore volumes. A MOP sponge-Ag heterogeneous catalyst (S-MOPS-Ag) was prepared by in-situ growth of silver nanoparticles inside the sulfur-functionalized MOP sponge by the reduction of Ag+ ions. The catalytic activity of S-MOPS-Ag was investigated for the reduction reaction of 4-nitrophenol in an aqueous condition. When S-MOPS-Ag was compressed and released during the reaction, the rate of the reaction was considerably increased. S-MOPS-Ag was easily removed from the reaction mixture owing to its monolithic character and was reused after washing and drying.
Lastly, compressible polyimide composite having metal binding sites was prepared by in situ polymerization inside a melamine sponge. 1,3,5-Tris(4-aminophenyl)benzene and pyromellitic dianhydride were used as a triamine and a dianhydride monomer, respectively, to construct the microporous framework, and 5-amino-1,10-phenanthroline was used as a functional monomer. The microporous polyimide containing phenanthroline groups (MPI-Phen) was obtained as insoluble powders. However, when the polymerization was carried out in the melamine sponge, MPI-Phen formed a coating layer on the sponge skeletons. The melamine sponge/microporous polyimide composite (MS/MPI-Phen) had an open cellular structure with a hierarchical porosity composed of macropores between the sponge skeletons and meso- and micropores of the MPI-Phen coating. It showed the higher compressive strength than the melamine sponge, indicating the reinforcement by the microporous polymer. The BET surface areas of MPI-Phen and MS/MPI-Phen were 723 m2g-1 and 524 m2g-1, respectively. Pd(II) ions were coordinated with the phenanthroline groups of MS/MPI-Phen for heterogeneous catalysis (MS/MPI-Phen-Pd). The catalytic activity of MS/MPI-Phen-Pd was evaluated for the Suzuki coupling reaction between bromobenzene and phenylboronic acid.
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dc.description.tableofcontentsChapterⅠ. Introduction 1
1.1 Microporous Organic Polymers(MOPs) 2
1.1.1 Introduction to MOPs 2
1.1.2 Preparation Methods of MOPs 3
1.1.2 Potential Applications of MOPs 13
1.2 Heterogeneous Catalysis with MOPs 20
1.2.1 Introduction to Heterogeneous Catalysis 20
1.2.2 Porous Materials for Heterogeneous Catalysis 22
1.2.3 Heterogeneous Catalysis with MOPs 23
1.3 Shape Control of MOPs 26
1.3.1 MOPs with Controlled Nanostructures 27
1.3.2 MOPs with Membrane Structures 28
1.3.3 MOPs with Monolithic Morphologies with Hierarchical Porosity 29
1.4 Electrospinning for Substrates 32
1.4.1 Introduction to Electrospinning 32
1.4.2 Electrospinning for Substrates of Functional Materials 35
1.4.3 Electrospinning for 3D Nanofibrous Structures 38
1.5 References 40
ChapterⅡ. Homogenized Electrospun Nanofiber Reinforced Microporous Polymer Sponge 49
2.1 Introduction 50
2.2 Experimental 52
2.3 Results and Discussion 56
2.3.1 Synthesis and the Morphology of the MOPs-Nanofiber Composites 56
2.3.2 Characterization of PVASi@TEDB-NH2 63
2.3.3 Porosity of PVASi@TEDB-NH2 66
2.3.4 Application of PVASi@TEDB-NH2 as Organic Dye Adsorbent 68
2.4 Conclusions 74
2.5 References 75
ChapterⅢ. Preparation of Microporous Polymer Membrane Containing Pd Nanoparticles as a Catalytic Membrane 81
3.1 Introduction 82
3.2 Experimental 84
3.3 Results and Discussion 88
3.3.1 Synthesis and Characterization of HCP-bases Microporous Membrane 88
3.3.2 Fabrication of a Pd-Containing Microporous Catalytic Membrane and Its Catalytic Ability 98
3.4 Conclusions 102
3.5 References 103
ChapterⅣ. Preparation of a Sulfur-functionalized Microporous Polymer Sponge and In Situ Growth of Sliver Nanoparticles: a Compressible Monolithic Catalyst 108
4.1 Introduction 109
4.2 Experimental 111
4.3 Results and Discussion 115
4.3.1 Synthesis and Characterization of a MOP Sponge 115
4.3.2 Functionalization of a MOP Nanotube Sponge with Sulfur Groups 119
4.3.3 A Sliver Decorated MOP Sponge as a Heterogeneous Catalyst 126
4.3.4 Catalytic Ability Evaluation of S-MOPS-Ag for the Reduction of 4-Nitrophenol 129
4.4 Conclusions 134
4.5 References 134
ChapterⅤ. A Hierarchically Porous Polyimide Composite Prepared by One-Step Condensation Reaction inside a Sponge For Hethrogeneous Catalysis 139
5.1 Introduction 140
5.2 Experimental 142
5.3 Results and Discussion 145
5.3.1 Synthesis and Characterizations of MPI-Phen 145
5.3.2 Fabrication and Characterizations of MS/MPI-phen 149
5.3.3 Pd2+ Chelating into MS/MPI-Phen for Suzuki Coupling Reaction 154
5.4 Conclusions 159
5.5 References 159
국문요약 165
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dc.formatapplication/pdf-
dc.format.extent6373028 bytes-
dc.format.mediumapplication/pdf-
dc.language.isoen-
dc.publisher서울대학교 대학원-
dc.subjectmicroporous polymer-
dc.subjectelectrospinning-
dc.subjectsponge-
dc.subjectmembrane-
dc.subjectheterogeneous catalysis-
dc.subjectdye adsorption-
dc.subject.ddc620.1-
dc.titlePreparation of Functional Microporous Organic Polymers and Their Applications for Heterogeneous Catalysis and Dye Adsorption-
dc.title.alternative기능성 마이크로기공성 유기고분자의 합성과 이의 불균질 촉매반응과 염료 흡착에의 활용-
dc.typeThesis-
dc.contributor.AlternativeAuthorJong Gil Kim-
dc.description.degreeDoctor-
dc.contributor.affiliation공과대학 재료공학부-
dc.date.awarded2017-08-
Appears in Collections:
College of Engineering/Engineering Practice School (공과대학/대학원)Dept. of Material Science and Engineering (재료공학부) Theses (Ph.D. / Sc.D._재료공학부)
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