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研究生： 江碩桓
Jiang, Shuo-Huan
論文名稱： 吡啶磷配位基的金屬錯化合物的產氫催化反應
Hydrogen Evolution Catalyzed by Metal complexes Bearing with Pyridylphosphine Ligands
指導教授： 許鏵芬
Hsu, Hua-Fen
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： 2020
畢業學年度： 108
語文別： 英文
論文頁數： 69
中文關鍵詞： 光催化產氫 、吡啶磷配位基 、鎳吡啶磷配位錯合物 、鈷吡啶磷配位錯合物
外文關鍵詞： photocatalytic hydrogen evolution, pyridylphosphine ligand, nickel complex, cobalt complex
相關次數： 點閱：101  下載：0 
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    • 現今無論是在工業原料上或是日常的電力來源，化石燃料都扮演著一個相當重要的角色，但也因為如此，大氣中二氧化碳的含量逐漸升高，所以對於現在的我們來說，發展一種可以替代再生更可以永續使用的能源方式是相當迫切的。基於這個原因，在這個研究中，我們嘗試開發可以藉由光催化來去產生氫氣的鎳以及鈷錯合物，我們利用了兩種吡啶磷配位基PN2 跟 PN2’ (PN2 = bis(2-picolyl)phenylphospphine), PN2’ =bis(6-methyl-2-picolyl)phenylphosphine，[[NiII(PN2)2][ClO4]2 ([1][ClO4]2), {[NiII(PN2’)2][ClO4]2 • 2.5CH3CN ([2][ClO4]2 • 2.5CH3CN) and [CoII(PN2’)2(C2H5CN)][ClO4]2 ([3][ClO4]2).，這些我們合成出的錯合物都透過X-光單晶繞射儀、元素分析、紫外-可見光-近紅外光光譜、核磁共振光譜以及循環伏安法進行分析與鑑定，並且也有對光催化產氫進行研究，發現錯合物2 利用酒精水溶液當溶劑的情況下，對於光催化的反應性在144小時下轉化數為2014，其反應性是在實驗室以往合成的錯合物中是最高的， 而且就算只在純水中也可以進行光催化(轉化數 172)

    Fossil fuels (gas, oil and coals) are energy carriers and raw materials for industry products for decades. Their combustion is contributed to CO2 rising level. Therefore, it is urgent to develop alternative, renewable and sustainable energy resources. In this research, we developed nickel and cobalt complexes with tridentate pyridylphosphine derivatives, PN2 and PN2’, as supporting ligands (PN2 = bis(2-picolyl)phenylphospphine), PN2’ = bis(6-methyl-2-picolyl)phenylphosphine). Three complexes have been obtained, [NiII(PN2)2][ClO4]2 ([1][ClO4]2), [NiII(PN2’)2][ClO4]2 • 2.5CH3CN ([2][ClO4]2 • 2.5CH3CN) and [CoII(PN2’)2(C2H5CN)][ClO4]2 ([3][ClO4]2). All of them have been characterized by X-ray crystallography, elemental analysis, UV-vis-NIR spectroscopy, NMR spectroscopy and cyclic voltammetry. Furthermore, the photocatalytic hydrogen evolution of theses complexes has been investigated. Complex 2 has the best catalytic efficiency among three in H2O/EtOH hybrid solution (TON = 2014 in 144 hours).

    Abstract III 摘要 IV 誌謝 V List of contents VI List of Schemes VIII List of Tables IX List of Figures X Abbreviations XIII Chapter 1 Introduction 1 1-1 Renewable energy 1 1-2 Photocatalytic and electrocatalytic hydrogen production system 1 1-3 Electrocatalytic hydrogen evolution system. 2 1-4 Photocatalytic hydrogen evolution system. 7 1-5 Motivation of this work 10 Chapter 2. Result and discussion 11 2-1. Synthesis and characterization of nickel complex 11 2-2 Synthesis and characterization of [NiII(PN2)2][ClO4]2 ([1][ClO4]2) 12 Synthesis. 12 Elemental analysis 12 The X-ray structure 13 Spectroscopic and electrochemical study. 16 2-3. Synthesis and characterization of [NiII(PN2’)2][ClO4]2 • 2.5CH3CN ([2][ClO4]2 • 2.5CH3CN) 20 Synthesis. 20 Elemental analysis 20 The X-ray structure 21 Spectroscopic and electrochemical study. 25 2-4. Synthesis and characterization of [CoII(PN2’)2(C2H5CN)][ClO4]2 ([3][ClO4]2) 30 Synthesis. 30 Elemental analysis 30 The X-ray structure 31 Spectroscopic and electrochemical study. 34 2-5 Photocatalytic hydrogen evolution 39 Chapter 3. Conclusions 45 Chapter 4. Experiments and Instruments 46 4-1 General procedures and materials. 46 4-2 Synthesis 47 Synthesis of bis(2-picolyl)phenylphosphine (PN2) 47 Synthesis of bis(6-methyl-2-picolyl)phenylphosphine (PN2’) 47 Synthesis of [NiII(PN2)2][ClO4]2 ([1][ClO4]2) 48 Synthesis of [NiII(PN2’)2][ClO4]2 • 2.5CH3CN ({[2][ClO4]2 • 2.5CH3CN) 48 Synthesis of [CoII(PN2’)2(C2H5CN)][ClO4]2 ([3][ClO4]2) 48 4-3 The study for Photocatalytic hydrogen evolution 49 4-4 Instrument 50 X-ray crystallographic data collection of the structures. 50 Elemental analysis. 50 UV-Vis-NIR spectroscopy. 50 Cyclic Voltammetry. 50 Nucleic Magnetic Resonance Spectroscopy. 51 Electron Magnetic Resonance Spectroscopy 51 Gas Chromatograph. 51 References 52 Appendix A 55 CIF check of [NiII(PN2)2][ClO4]2 ([1][ClO4]2) 55 Appendix B 58 CIF check of [NiII(PN2’)2][ClO4]2 • 2.5MeCN ([2][ClO4]2 • 2.5CH3CN) 58 Appendix C 62 CIF check of [CoII(PN2’)2(C2H5CN)][ClO4]2 ([3][ClO4]2) 62 Appendix D 65 Appendix E 67

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