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Synthesis Of Poly(Vinylpyrrolidone) (Pvp) Grafted Silica As Matrix For Generation Of Palladium Nanoparticles And Investigation Of Effect Of Graft Lengths On Catalytic Activity

dc.contributor.advisorBarsbay, Murat
dc.contributor.authorÇaylan, Tansu
dc.date.accessioned2019-10-11T10:20:58Z
dc.date.issued2019
dc.date.submitted2019-09-13
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dc.identifier.urihttp://hdl.handle.net/11655/9198
dc.description.abstractThe rationale of M.S thesis work is to investigate the effect of chain length of the stabilizing polymer brushes attached to silica surface on the formation of metallic palladium nanoparticles (NPs) and their catalytic activity. Poly(vinyl pyrrolidone) (PVP) brushes forming a very thin shell was grafted from silica microparticles (Si@PVP) via RAFT mediated graft polymerization method thus controlling the molecular weights and structures of PVP grafts. Palladium (Pd) nanoparticles were formed in PVP stabilizing matrix by gamma radiolysis of Pd(Ⅱ) ions to yield Pd(0) decorated core-shell particles (Si@PVP-PdNP). Size Exclusion Chromatography (SEC) and Thermogravimetric Analysis (TGA) results indicated the formation of PVP brushes with different molecular weights on silica. Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM) measurements revealed that increased molecular weight of PVP brushes sterically blocked the particle growth and yielded more small Pd nanoparticles rather than fewer large ones. Si@PVP-PdNP having different PVP lengths and Pd sizes were evaluated for their catalytic activity and reusability in the model reduction of 4-nitrophenol to 4-aminophenol. It has been found that longer grafts are more effective in preventing NPs from leaking into the solution through the PVP shell, even if nanoparticles (NPs) are smaller in their presence, yet they allow the diffusion of reactants, resulting in more stable catalytic activity in repeated measurement cycles. On the other hand, short grafts are not sufficiently effective in preventing NP agglomeration and leakage. These findings are particularly important for heterogeneous catalyst systems in that they show the effects of surface-bound polymeric stabilizers on NP formation and catalytic activity. Keywords: Surface modification, Silica micro-particles, RAFT polymerization, Palladium nanoparticles.tr_TR
dc.description.tableofcontentsTABLE OF CONTENTS ABSTRACT ÖZET ACKNOWLEDGEMENTS TABLE OF CONTENTS FIGURES LIST OF TABLES LIST OF ABBREVIATIONS 1. INTRODUCTION 2. GENERAL INFORMATION 2.1. Surface Modification 2.1.1. Graft Polymerization 2.1.1.1. Surface Functionalization in a Controlled-manner 2.2. Controlled/living Radical Polymerization (CRP) Techniques 2.2.1. Atom Transfer Radical Polymerization (ATRP) 2.2.2. Nitroxide-Mediated Polymerization (NMP) 2.2.3. Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) 2.3. Surface Functionalization via RAFT Mediated Graft Polymerization and Stabilizing Effect of Surface-attached Grafts 2.4. Metal Nanoparticles and Their Stabilization 2.5. Preparation of Metal Nanoparticles by Ionizing Radiation 2.5.1. The Effect of Radiation Dose Rate and Absorbed Dose 3. EXPERIMENTAL 3.1. Materials 3.2. Attenuated Total Reflectance Fourier Transform Infra-Red (ATR-FTIR) Spectroscopy 3.3. X-Ray Photoelectron Spectroscopy (XPS) 3.4. UV–Vis Spectropcopy 3.5. Dynamic Light-Scattering (DLS) 3.6. Atomic Force Microscopy (AFM) 3.7. Scanning Electron Microscopy (SEM) Imaging and Energy Dispersive X-Ray (EDX) Mapping 3.8. Transmission Electron Microscopy (TEM) 3.9. Size Exclusion Chromatography (SEC) Analysis 3.10. Thermogravimetric Analysis (TGA) 3.11. Synthesis of 4,4'-Azobis(4-cyanopentanoic acid) (ACPA) Functionalized Silica (Si@ACPA) 3.12. Synthesis of Poly(vinylpyrrolidone) (PVP) Grafted Silica Micro-particles (Si@PVP) 3.13. Formation of Palladium Nanoparticles Stabilized by PVP (Si@PVP-PdNP) 3.14. Catalytic Activity Measurements 4. RESULT AND DISCUSSION 5. CONCLUSION REFERENCES CURRICULUM VITAEtr_TR
dc.language.isoentr_TR
dc.publisherFen Bilimleri Enstitüsütr_TR
dc.rightsinfo:eu-repo/semantics/openAccesstr_TR
dc.subjectSurface modificationtr_eng
dc.subjectSilica micro-particlestr_eng
dc.subjectRAFT polymerizationtr_eng
dc.subjectPalladium nanoparticlestr_eng
dc.subjectGraft polymerizationtr_eng
dc.subjectMetal Nanoparticles and their stabilizationtr_eng
dc.subject.lcshyüzey modifikasyonutr_TR
dc.subject.lcshpolimerizasyontr_TR
dc.titleSynthesis Of Poly(Vinylpyrrolidone) (Pvp) Grafted Silica As Matrix For Generation Of Palladium Nanoparticles And Investigation Of Effect Of Graft Lengths On Catalytic Activitytr_eng
dc.title.alternativePaladyum Nanoparçacıkların Üretimi İçin Matris Olarak Poli(Vinilpirolidon) (Pvp) Aşılanmış Silika Sentezi ve Aşı Uzunluklarının Katalitik Aktiviteye Etkisinin Araştırılmasıtr_TR
dc.typeinfo:eu-repo/semantics/masterThesistr_TR
dc.description.ozetBu tez çalışmanın amacı, silika yüzeyine bağlı stabilize edici polimer fırçaların zincir uzunluğunun, metalik paladyum nanopartiküllerinin (NP'ler) oluşumu ve katalitik aktivitesi üzerindeki etkisini araştırmaktır. Çok ince bir kabuk oluşturan poli(vinil pirolidon) (PVP) fırçalar, silika mikropartiküllerinden Tersinir Eklenme Parçalanma Zincir Transferi (RAFT) aracılı aşı polimerizasyonu yöntemiyle aşılanmış (Si@PVP), böylece PVP aşıların moleküler ağırlıkları ve yapıları kontrol edilmiştir. PVP stabilize edici matris içinde paladyum Pd(Ⅱ) iyonlarının gamma radyolizi ile metalik Pd(0)’a indirgenmesi sayesinde, Pd nanoparçacıkları ile dekore edilmiş çekirdek-kabuk formunda parçacıklar (Si@PVP-PdNP) elde edilmiştir. Büyüklükçe Ayırma Kromotografisi (BAK) ve Termogravimetrik Analiz (TGA) sonuçları silika üzerinde farklı molekül ağırlıklarına sahip PVP fırçalarının oluştuğuna yönelik sonuçlar vermiştir. Dinamik Işık Saçılımı (DLS) ve Geçirimli Elektron Mikroskopisi (TEM) ölçümleri, artan PVP aşı uzunluklarının, Pd nanoparçacılarının büyümesini sterik olarak engelleyerek daha fazla sayıda küçük Pd nanoparçacıklarının oluşumuna sebep olduğunu görtermiştir. Farklı PVP uzunluklarına ve Pd nanoparçacık boyutlarına sahip olan Si@PVP-PdNP örnekleri, model olarak seçilen 4-nitrofenol’ün 4-aminofenol’e indirgenme reaksiyonunda katalitik aktiviteleri ve yeniden kullanılabilirlikleri açısından değerlendirilmiştir. Yüksek mol kütleli polimer zincirlerinin aşılandığı yapılarda daha küçük nanoparçacıklar oluşsa da, uzun aşı zincirlerinin bu nanoparçacıkların çözeltiye sızmalarını sterik olarak önlemede daha etkili oldukları, ancak yine de reaktiflerin difüzyonuna izin vermeleri sayesinde tekrarlanan ölçüm döngülerinde daha kararlı aktivite sağladıkları görülmüştür. Öte yandan, kısa aşı zincirlerinin nanoparçacıkların aglomerasyonunu ve sızıntısını önlemede yeterince etkili olmadıkları ortaya konmuştur. Bu bulgular, yüzeye bağlı polimerik stabilizatörlerin, özellikle heterojen katalizör sistemlerinde kullanımlarında, nanoparçacık oluşumu ve katalitik aktivite üzerinde etkilerini göstermeleri bakımından önemlidir. Anahtar Sözcükler: Yüzey modifikasyonu, Silika mikro-parçacıklar, RAFT polimerizasyonu, Paladyum nanoparçacıklar.tr_TR
dc.contributor.departmentKimyatr_TR
dc.embargo.terms6 aytr_TR
dc.embargo.lift2020-04-14T10:20:58Z
dc.fundingYoktr_TR


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