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dc.description.abstractThe Grubbs-Hoveyda-type Ru-carbene complex was immobilized onto the ionic multi-walled carbon nanotubes (IM-f-MWCNTs), which were functionalized with imidazolium salts bearing bromide or PF6 anions. In order to immobilized the Ru-carbene complex, the MWCNT surface was covalently modified with 3-propylimidazole through the oxidation followed by amide bond formation with 3-aminopropylimidazole. The imidazole-functionalized MWCNTs were reacted with pre-synthesized 1-[2-(6-bromohexyloxy)-1-methylethoxy]-2-propenylbenzene to link the chelating propenylbenzene moiety to CNT-surface with imidazolium bromide linker. The PF6 anion was introduced via anion exchange with NaPF6. The metathesis with Grubbs’ second generation Ru-carbene complex afforded IM-f-MWCNT-supported Ru-carbene complexes. TEM, SEM, XPS, and XRD analysis clearly indicated anchoring of Ru-carbene complex onto the imidazolium salt-functionalized ionic MWCNTs. The ionic CNT-supported Ru-carbene complexes showed high dispersity in methylene chloride and ionic liquid. The RCMs of various dienes using 2.5 mol % of IM-f-MWCNT-supported Ru-carbene complex were carried out in methylene chloride with >99% conversion. The IM-f-MWCNT-supported Ru-carbene complex can be recovered and reused 10 times without significant loss of catalytic activity. Similar catalytic activity and recyclability were observed when the RCMs were carried out in an ionic liquid, [bmim][PF6]. Tandem catalytic reaction has become increasingly important. Many successful examples of tandem processes have been developed, including ruthenium-catalyzed metathesis followed either by hydrogenation, Diels-Alder reaction, dihydroxylation etc. In previous works, it has been developed that the functionalization of MWCNTs with imidazolium salt, an ionic liquid moiety, could facilitate the immobilization of Pd NPs. In addition, the supported Hoveyda-type Ru-carbene complexes tethering imidazolium tags at chelating isopropoxy group, respectively. On the basis of these results, it can be expected that immobilization of both Pd nanparticle catalyst and Ru-carbene complex onto the ionic CNTs could provides an immobilized dual-functional catalyst that allow tandem catalytic ring-closing metathesis/hydrogenation. In this work, the dual-function CNT-supported Pd NPs/Ru-carbene catalyst were prepared, and investigated it catalytic activity in tandem ring-closing metathesis/hydrogenation of dienes. Although their catalytic activity and recyclability is not sufficiently high, the developed CNT-supported dual-functional Ru-carbene/Pd nanoparticle catalyst demonstrated the possibility for the development of supported dual-function catalyst for tandem reactions.;이 논문은 크게 두 가지의 주제로 구성되어 있다. Part Ⅰ은 Ring-Closing Metathesis(RCM)를 위한 Ionic linker를 가진 Ru-Carbene Complex로서 CNT에 고정화 되어 있는 촉매에 관한 내용이고, Part Ⅱ는 RCM와 Hydrogenation을 연속해서 반응하기 위해 CNT라는 지지체 위에 Ru-carbene과 Pd nanoparticle을 동시에 얹은 Dual-funtional catalyst에 관한 내용으로 이루어져 있다. Part Ⅰ : 탄소나노튜브(Carbon Nanotube)는 나노 물질로서 저가이면서 화학적 안정성이 높고, π 전자가 풍부하여 전기화학 분야 등에서 연구가 활성화 되어 있다. 이와 같은 특성을 지닌 탄소나노튜브의 표면 개질을 바꾸는 방법에 대한 연구를 축적하여 왔고 그 과정에서 이미다졸염의 음이온을 다양한 종류로 변화시켜 이온성 액체에서의 영향을 연구하여 왔다. 이러한 연구 결과를 바탕으로 본 연구에서는 이온성 나노소재에 Ru-carbene을 고정화 할 경우 homogeneous한 반응조건에서와 동일하게 RCM이 가능하며, 탄소나노튜브라는 지지체로 인해 촉매반응이 끝난 후에도 촉매의 회수 및 재사용이 용이할 것이라는 가정하에 고정화 촉매를 개발하였다. 개발된 촉매는 활성이 매우 좋아 유기 용매인 dichloromethane과 이온성 액체 모두에서 10번 이상 재사용 되는 효능을 보였고, 비교적 안정하다는 것을 확인할 수 있었다. Part Ⅱ : 파트 2에서는 파트 1에서 보여준 높은 활성의 CNT-supported Ru-carbene 촉매에서 나아가 탄소나노튜브를 지지체로 사용하여 Ru-carbene과 Pd nanoparticle을 동시에 얹어 두 가지의 기능을 하는 촉매의 개발에 대한 내용을 다루 었다. 수소 기체 하에 Pd을 immobilization하는 과정이 추가되므로 실제 dualfunctional catalyst를 만드는 방법은 위의 파트 1의 촉매 합성 방법과는 달라진다. 여러 단계를 거쳐 한 지지체 위에 두 가지 종류의 금속을 동시에 immobilization하여 촉매를 만들 수 있었고, 실제 탄소나노튜브에 고정화된 이중 기능 촉매를 사용하여 Ring-Closing Metathesis와 Hydrogenation을 연속해서 가능하게 할 수 있었다.-
dc.description.tableofcontentsPART I. The Ionic CNT-Supported Ru-Carbene Complex for Ring-Closing Metathesis 1 Abstract 2 Ⅰ. Introduction 3 Ⅱ. Experimental Section 6 Ⅱ-1. Materials 6 Ⅱ-2. Sample Preparation 7 Ⅱ-2-1. Preparation of Carboxylic Acid-functionalized Carbon Nanotube (CNT-COOH) 7 Ⅱ-2-2. Preparation of the Imidazole-functionalized Carbon Nanotubes (IM-f-CNTs) 7 Ⅱ-2-3. Synthesis of 2-(2-Propenylphenoxy)propionic Acid Methyl Ester 8 Ⅱ-2-4. Synthesis of 2-(2-Propenylphenoxy)propan-1-ol 9 Ⅱ-2-5. Synthesis of 1-[2-(6-bromohexyloxy)-1-methylethoxy]-2-propenylbenzene 9 Ⅱ-2-6. Imidazolium Bromide-functionalized MWCNTs 10 Ⅱ-2-7. Immobilization of Hoveyda-type Ruthenium-Carbene Complex onto IM-f-MWCNTs having bromide 10 Ⅱ-2-8. General Methods for Ring-Closing Metathesis of Dienes 5 using Catalyst 4 11 Ⅱ-2-9. General Procedure for Catalyst Recycling Experiment. 12 Ⅱ-3. Measurement 12 Ⅲ. Results & Discussion 14 Ⅳ. Conclusion 40 Ⅴ. References 41 PART II. The CNT-Supported Dual-Functional Ru-Carbene/Pd Nanoparticle Catalyst for Tandem Ring-Closing Metathesis and Hydrogenation Reaction 44 Abstract 45 Ⅰ. Introduction 46 Ⅱ. Experimental Section 49 Ⅱ-1. Materials 49 Ⅱ-2. Sample Preparation 49 Ⅱ-2-1. Preparation of Carboxylic Acid-functionalized Carbon Nanotube (CNT-COOH) 49 Ⅱ-2-2. Preparation of the Imidazole-functionalized Carbon Nanotubes (IM-f-CNTs) 50 Ⅱ-2-3. 3-Methyl-1-[2-(2-propenylphenoxy)]propyl-3H-imidazolium Bromide 50 Ⅱ-2-4. Imidazolium Ion-tagged Ru-Carbene Complexes 51 Ⅱ-2-5. Imidazolium-f-CNT Hydrochloric Acid Salt 52 Ⅱ-2-6. Palladium Nanoparticles-supported onto IM -f-CNT Hydrochloric Acid Salt 52 Ⅱ-2-7. Pd/IM-f-CNT 53 Ⅱ-2-8. Pd/Imidazolium Bromide-functionalized MWCNTs 53 Ⅱ-2-9. Pd/Imidazolium Bromide-functionalized CNT-supported Ru Carbene Catalyst 53 Ⅱ-2-10. General Methods for Ring-Closing Metathesis and Hydrogenation of Dienes 12 using Catalyst 11 54 Ⅱ-3. Measurement 55 Ⅲ. Results & Discussion 56 Ⅳ. Conclusion 79 Ⅴ. References 80 Abstract in Korean (국문 초록) 81-
dc.format.extent11910421 bytes-
dc.publisher이화여자대학교 대학원-
dc.titleDevelopment of the Ionic CNT-supported Bifunctional Ru/Pd Catalyst for Tandem Ring-Closing Metathesis/Hydrogenation-
dc.typeMaster's Thesis-
dc.format.pagevii, 83 p.-
dc.identifier.major대학원 화학·나노과학과- 2-
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