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研究生： 黃靖雅
Ching-Ya Huang
論文名稱： 以一步合成法製備含鈀奈米金屬之中孔洞二氧化矽及其鑑定
Preparation and Characterization of Pd-containing Mesoporous SiO2 by One-pot Synthesis
指導教授： 趙桂蓉
Kuei-Jung Chao
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2007
畢業學年度： 95
語文別： 英文
論文頁數： 89
中文關鍵詞： 中孔洞 、二氧化矽 、鈀 、一步合成 、共合成
外文關鍵詞： mesoporous, MCM-41, Pd, palladium, one-pot synthesis, co-synthesis
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    • This thesis includes the review on the recent progress of mesoporous silicas and metal-containing mesoporous materials as well as the report on preparation and characterization of highly dispersed palladium nanoparticles containing mesoporous silicas MCM-41 and MCM-48 which were prepared through one-pot synthesis. The complex-surfactant aggregates [CTA]2[PdBr4] were considered to be generated in the presence of a large amount of CTAB. The synthesis of MCM-41 mesophase templated by CTA+ surfactant and the generation of PdO species through the reaction between [PdBr4]2□ and hydroxide anion may occur simultaneously. Those PdO nanoparticles were reduced to Pd metal by hydrogen treatment and found to stay inside the mesochannels of MCM-41 as detected by TEM, XAS, and PXRD. In hydrothermal synthesis of Pd/MCM-48, Pd nanoparticles of average size 7 nm were found to be deposited on the MCM-48, probably derived from ethanol reduction of Pd (II) complex. Moreover, the template removal from MCM-41 was observed to be catalyzed by Pd(0) nanoparticles.

    Contents Chapter 1 Introduction 1 1.1 Mesoporous Silica Materials 1 1.1.1 Definition 1 1.1.2 Formation mechanism 2 1.2 Metal in Mesoporous Silicas 8 1.2.1 Post-synthesis 8 1.2.2 Co-synthesis 12 1.3 Template removal from mesoporous silica 17 1.4 The purpose of this study 23 1.5 References 25 Chapter 2 Experiment 29 2.2 Synthesis 30 2.2.1 MCM-41 30 2.2.2 Pd/MCM-41 30 2.2.3 MCM-48 33 2.2.4 Pd/MCM-48 34 2.2.5 Pd(BC) 35 2.3 Characterization 36 2.3.1 Inductive-coupling plasma-atomic emission spectroscopy analysis (ICP-AES) 36 2.3.2 Transmission electron microscopy analysis (TEM) 36 2.3.3 Fourier Transform Infrared Spectroscopy measurement (FT-IR) 37 2.3.4 X-ray diffraction measurement 38 2.3.5 Nitrogen adsorption/desorption measurement 39 2.3.6 X-ray absorption spectroscopy (XAS) measurement 40 2.3.7 Temperature programmed reduction (TPR) analysis 41 2.3.8 Thermal gravimetric analysis (TGA) 42 2.4 References 43 Chapter 3 Results and Discussion 44 3.1 The meso-structured phases of MCM-41 44 3.1.1 The structure of MCM-41 mesophase 44 3.1.2 The pore properties of MCM-41 phase 47 3.2 The mesostructured phase of MCM-48 50 3.3 The Pd species in Pd/MCM-41 and Pd/MCM-48 52 3.3.1 As-synthesized Pd/MCM-41 and Pd/MCM-48 52 3.3.2 Reduced Pd/MCM-41s 57 3.3.2.1 XRD analysis 57 3.3.2.2 TPR analysis 59 3.3.2.3 In-situ XAS 61 3.3.3 TEM 64 3.4 The formation mechanism of Pd(0) and PdO in Pd/MCM-41 and Pd/MCM-48 68 3.4.1 Pd/MCM-41 68 3.4.2 Pd/MCM-48 71 3.5 The template removal from Pd/MCM-41 73 3.5.1 TGA analysis of MCM-41as and Pd/MCM-41as 73 3.5.2 TGA of H2 pretreated Pd/MCM-41 and MCM-41 75 3.5.3 FT-IR study on MCM-41s and Pd/MCM-41s 79 3.6 References 82 Chapter 4 Conclusion 84 Chapter 5 Appendixes 85 Appendix I 85 Appendix II 87 Appendix III 89

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