目录／Contents
Chapter 1 Ionic Liquids1
1.1 Ionic liquids2
1.1.1 Definition2
1.1.2 A brief history of ionic liquids3
1.2 Properties of ionic liquids4
1.2.1 Why are ionic liquids liquid4
1.2.2 Viscosity4
1.2.3 Low volatility5
1.2.4 Conductivity6
1.2.5 Solvation properties6
1.3 Synthesis of ionic liquids7
1.3.1 Materials7
1.3.2 Instrumentation7
1.3.3 Imidazolium-based ionic liquids8
1.3.4 Pyrrolidinium-based ionic liquids14
1.3.5 Pyridinium-based ionic liquids19
1.4 Dissolution of metal catalysts in ionic liquids25
1.4.1 The addition of phosphine ligands25
1.4.2 The formation of phosphineimidazolylidene palladium complexes26
1.5 Ionic liquids analysed in this book26
1.6 Catalysis in ionic liquids27
References28
Chapter 2 X-ray Photoelectron Spectroscopy36
2.1 X-ray photoelectron spectroscopy36
2.1.1 Principle36
2.1.2 Experimental set-up38
2.1.3 Vacuum environment39
2.1.4 Charge neutralisation39
2.1.5 Data interpretation40
2.2 XPS experiment41
2.2.1 Instrument 41
2.2.2 Sample preparation and transfer43
2.2.3 Information depth43
2.2.4 Data processing43
2.2.5 XP Spectrum44
2.2.6 XPS analysis46
2.2.7 Charge correction47
2.2.8 Auger Parameter48
2.3 XPS of ionic liquids49
References50
Chapter 3 XPS of Pure Ionic Liquids and Ionic Liquid Mixtures54
3.1 Introduction54
3.2 Varying the cation56
3.2.1 Imidazolium-based ionic liquids56
3.2.2 Pyrrolidinium-based ionic liquids58
3.2.3 Pyridinium-based ionic liquids65
3.2.4 Comparison of imidazolium, pyrrolidinium and pyridiniumbased ionic liquids69
3.3 Varying the anion72
3.3.1 Acetate-based imidazolium ionic liquids72
3.3.2 Effect of the anion on the cation79
3.4 Ionic liquid mixture81
3.4.1 Imidazolium-based ionic liquid mixture81
3.4.2 Pyrrolidinium-based ionic liquid mixture 84
3.4.3 Pyridinium-based ionic liquid mixture85
3.5 Conclusions86
References87
Chapter 4 XPS of Solute-solvent Interaction in Ionic Liquids 93
4.1 Introduction93
4.2 Formation of a phosphineimidazolylidene palladium complex95
4.3 Pd as a probe of solute-solvent interactions102
4.4 Selection of anions： correlation of binding energy to established metrics 105
4.5 Can the solvent environment be tuned108
4.6 Can anion basicity impact on the reaction rate110
4.6.1 Suzuki cross coupling reaction111
4.6.2 Correlation of binding energy with reaction rate111
4.6.3 The catalytic activity of the palladium centre inionic liquid mixture114
4.7 Conclusions114
References115
Chapter 5 XPS of Metal-ligand Interaction in Ionic Liquids 123
5.1 Introduction123
5.2 Detection of the rhodium centre in solution125
5.3 Formation of the mono-phosphine rhodium complex 128
5.4 Investigation of the chelated diphosphine rhodium complex131
5.5 Correlation of reaction selectivity and binding energy 133
5.6 Conclusions135
References136
Appendix XP Spectra142
目录
第1章离子液体1
1.1 离子液体简介2
1.1.1 定义2
1.1.2 离子液体发展简史3
1.2 离子液体性能4
1.2.1 熔点4
1.2.2 粘度4
1.2.3 低挥发性5
1.2.4 导电性6
1.2.5 溶剂化性能6
1.3 离子液体合成7
1.3.1 原材料7
1.3.2 仪器表征7
1.3.3 咪唑类离子液体8
1.3.4 吡咯类离子液体14
1.3.5 吡啶类离子液体19
1.4 金属催化剂在离子液体中的溶解25
1.4.1 含磷配体体系25
1.4.2 钯－卡宾体系26
1.5 本书中应用的离子液体26
1.6 离子液体中的催化反应27
参考文献28
第2章X射线光电子能谱36
2.1 X射线光电子能谱36
2.1.1 原理36
2.1.2 实验参数设定38
2.1.3 真空39
2.1.4 电荷中和39
2.1.5 数据处理40
2.2 X射线光电子能谱实验41
2.2.1 仪器41
2.2.2 样品43
2.2.3 检测厚度43
2.2.4 数据分析43
2.2.5 能谱谱图44
2.2.6 谱图分析46
2.2.7 电荷校准47
2.2.8 俄歇参数48
2.3 离子液体的X射线光电子能谱49
参考文献50
第3章纯离子液体体系54
3.1 前言54
3.2 阳离子的影响56
3.2.1 咪唑类离子液体56
3.2.2 吡咯类离子液体58
3.2.3 吡啶类离子液体65
3.2.4 三种体系的对比69
3.3 阴离子的影响72
3.3.1 醋酸型离子液体72
3.3.2 阴离子对阳离子的影响79
3.4 二元混合体系81
3.4.1咪唑类二元混合物81
3.4.2吡咯类二元混合物84
3.4.3吡啶类二元混合物85
3.5 小结86
参考文献87
第4章离子液体中的溶质－溶剂相互作用93
4.1 前言93
4.2 钯－卡宾体系95
4.3 溶质－溶剂相互作用102
4.4 阴离子的影响105
4.5 溶剂的影响108
4.6 阴离子的碱性对反应速率的影响110
4.6.1 铃木反应111
4.6.2 反应速率－结合能111
4.6.3 二元混和体系114
4.7 小结114
参考文献115
第5章离子液体中的金属－配体相互作用123
5.1 前言123
5.2 金属铑体系125
5.3 含磷配合体系128
5.4 螯合型含磷配合体系131
5.5 反应选择性－结合能133
5.6 小结135
参考文献136
附录AX射线光电子能谱谱图142
內容試閱：
PrefaceThis book is written based upon the research work being conducted by Dr. Yanhui Liu, Prof. Jinglong Gao and myself all from Shenyang Ligong University. The commencement of this project dates back to the year of 2008, when I firstly joined the Nottingham Ionic Liquids group. Throughout the whole of my Ph.D study, many attempts had been made with the view of demonstrating the electronic environment of ionic liquids by the state-of-the-art ultra high vacuum technique, X-ray photoelectron spectroscopy. I was a bit of luck to have finally systematically investigated three families of ionic liquids, including imidazolium, pyrrolidinium and pyridinium, as well as directly probed the interaction of solute-solvent and solute-ligand in ionic liquids. I was delighted to see these studies had made this field expanded and matured.It was in the year of 2012, when Dr. Liu and I founded the Ionic Liquid Group at Shenyang Ligong University. I am fortunate to have collaborated with Dr. Liu, who has shown strong background in theory and great intelligence in doing research. With her tremendous helps, I am flattered to see we could add something to this research area. The recent publishing of the paper about the impact of the cation acidity on the cation-anion interaction in ionic liquids inspires us to finish this book, which summarily describes all aspects of our research with reference to ionicliquids.Herein, we bring all results together in a coherent and smooth account of the field in simple words. Chapter 1 and Chapter 2, which briefly introduce the basic aspects of ionic liquids and the XPS technique respectively, were written by Dr. Liu. One of the results chapters, Chapter 5, was also written by Dr. Liu. I wrote two of the results chapters, Chapter 3 and Chapter 4. The Appendix chapter, which demonstrates XP spectra for all ionic liquids studied in this book was written by Prof. Gao. We hope some may read this book for basic understanding, some for further improvement and some for enjoyment.So many people helped me in this project, whom if I do not show my appreciation, I will be failing in my duty. To Prof. Peter Licence who is my academic Ph.D supervisor and the person I respect the most, I owe my biggest debt grateful. His wisdom and encouragement is always a constant source of motivation throughout the whole of my research life. Furthermore, I am on behalf of Dr. Liu to acknowledge the International Cooperation Project F16-214-6-00 from the Department of Science and Technology of City of Shenyang for financial support. Last but not least, I must thank Dr. Liu and Prof. Gao once again, for spending several months with me in front of the laptop preparing this book.Men ShuangNovember 19th 2017前言离子液体主要是指完全由有机阳离子，以及无机或有机阴离子组成的，在室温或接近室温下呈现出液体状态的熔融盐类。离子液体具有不易挥发、无污染、不易燃、易与产物分离、易回收、可循环使用以及使用方便等优点，是传统有机溶剂的理想替代品。它有效地避免了传统有机溶剂造成的环境污染、健康受损、安全隐患以及设备腐蚀等问题，是名副其实的、环境友好的绿色溶剂，适应清洁技术和可持续发展的要求。近年来，离子液体的应用已经处于工业试验阶段，即将进入工业应用；另一方面因为离子液体种类繁多，每一种化学反应在离子液体中进行都有可能取得与传统方法不同的、令人惊异的结果，这一巨大的化学新宝藏有待我们去开发。笔者所在课题组近几年来以咪唑类离子液体为突破口，一直从事离子液体的合成、提纯、表征及应用研究。本书不仅介绍了课题组成员的大量研究结果，也介绍了相关基本的知识。这包括从光电子能谱角度，揭示了离子液体结构与性能间的关系；在对离子液体进行系统详细阐述的同时，也对离子液体中的催化剂体系进行了初步介绍。本书分为6章，第1章、第2章和第5章由沈阳理工大学刘艳辉博士编写，第3章和第4章由沈阳理工大学门爽博士编写，附录由沈阳理工大学高景龙教授及高级实验师编写。本书的出版得到了沈阳理工大学学科发展规划处学术专著基金和沈阳市科技局国际合作处国际合作项目（F16-214-6-00）的共同资助。在本书的编写过程中，英国诺丁汉大学Peter Licence教授给予了指导和支持，电子工业出版社有关同志为本书的顺利出版付出了辛勤的劳动，在此一并表示诚挚的谢意！由于离子液体领域的研究正在蓬勃发展，知识体系更新迅速，而且以X射线光电子能谱手段研究离子液体的结构性能是一种崭新的技术，加上笔者所在的课题组成员水平所限，成书难免会有不足之处，敬请广大读者批评指正。刘艳辉2017年12月于沈阳理工大学
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