- 學位論文
官能化離子液體與紫精化合物之合成以開發具分子感測與電致色變應用性之電聚合高分子修飾電極
Synthesis of functionalized ionic liquids and viologen compounds for the development of electropolymerized polymer-modified electrodes with wide applications from molecular sensing to electrochromism
摘要
ABSTRACT My graduate research at KMU is focused on the synthesis of a new class of ionic liquids which can be functionalized using specific groups to enhance the properties of ionic liquids and to meet multitasking ability in order to achieve wide range of application such as molecular sensors, electrochromism and solvatochromism. Hereby, our first report (shown in chapter 2) is focused on electropolymerizable carbazole-functionalized imidazolium and pyridinium-based ionic liquids (ILs); the monomers of which were synthesized and characterized using 1H, 13C, 19F NMR, and ESI-MS. They were electropolymerized onto indium tinoxide (ITO) electrodes via cyclic voltammetric polymerization in several selected room temperature ILs (RTILs) as well as in conventional organic solvents. Two redox couples, corresponding to the monomer and oligomer/polymer, respectively, of the carbazole-functionalized ILs, were observed during the cyclic voltammetric polymerization. It was found, as common ILs, that the anionic components exhibit crucial effects on the physicochemical properties of the carbazole-functionalized ILs. The anions of which actually were replaced by the anions of the electrolytes in which the monomers were dissolved. The RTILs used for the electropolymerization thus determined the electrochemical behavior of the monomers, surface morphologies and the physicochemical properties of the poly(ILs) films. After the modification of ITO electrodes with poly(ILs), the electrochemical performance of the semiconducting electrodes was significantly improved towards uric acid oxidation. The poly(ILs) show adjustable properties (via changing counter anions), and exhibit a wide range of solubility in organic solvents, and electrochromic and solvatochromic properties. The second report (shown in chapter 3) is focused on mono- and di-carbazole functionalized viologen compounds, which were characterized using 1H, 13C, 19F NMR, and ESI-MS. Suitable cyclic voltammetric techniques were developed to polymerize these compounds on the ITO and glassy carbon (GC) electrode through a radical-induced polymerization triggered by electrochemical oxidation of carbazole moieties in electrolytes composed of NaClO4/acetonitrile or room temperature ionic liquid/organic solvents (acetonitrile, propylene carbonate). The basic physical properties and reactivity of these polymers were studied. It was found that the properties of the electropolymerized polymers were crucially controlled by the chemical structure of the monomer and the electrolyte compositions. The polymer films showed electrochromic behavior, and the color changed from greenish at the potential where carbazole groups were oxidized to violet or colorless at which reduction of viologen groups occurred; violet or colorless depended on which of the two reductive states of the viologen moieties was reached. The polymer films were capable of enhancing the oxidative current of uric acid and ascorbic acid, respectively, in neutral media, which might be due to the concentrating ability of the viologen moieties towards negatively charged species such as ferricyanide ([Fe(CN)6]3−) and ferrocyanide ([Fe(CN)6]2−). The third report (shown in chapter 4) is focused on study of di-carbazole functionalized viologen compounds, cyclic voltammetric techniques were developed to polymerize these compounds on glassy carbon (GC) electrode through a radical-induced polymerization by electrochemical oxidation of carbazole moieties in electrolytes composed of room temperature ionic liquid/organic solvents (propylene carbonate). It was found that the properties of the electropolymerized polymers can be enhanced by chemically fabricating metal nano particles on surface of the polymer by adsorption or deposition. The modified polymer electrode enhances the rate of electro chemical oxidation reaction. In summary, my PhD program mainly contributes to develop a new type of ionic liquids and ionic compounds. Different polymerization techniques have been developed to polymerize these compounds on electrode surface using ionic liquids and organic solvents. These compounds were characterized and their physical properties were studied. The results from these studies have allowed us to develop interesting application such as sensors, electrochromism and solvatochromism. In future will help us to broaden their application towards energy storage application.
並列摘要
ABSTRACT My graduate research at KMU is focused on the synthesis of a new class of ionic liquids which can be functionalized using specific groups to enhance the properties of ionic liquids and to meet multitasking ability in order to achieve wide range of application such as molecular sensors, electrochromism and solvatochromism. Hereby, our first report (shown in chapter 2) is focused on electropolymerizable carbazole-functionalized imidazolium and pyridinium-based ionic liquids (ILs); the monomers of which were synthesized and characterized using 1H, 13C, 19F NMR, and ESI-MS. They were electropolymerized onto indium tinoxide (ITO) electrodes via cyclic voltammetric polymerization in several selected room temperature ILs (RTILs) as well as in conventional organic solvents. Two redox couples, corresponding to the monomer and oligomer/polymer, respectively, of the carbazole-functionalized ILs, were observed during the cyclic voltammetric polymerization. It was found, as common ILs, that the anionic components exhibit crucial effects on the physicochemical properties of the carbazole-functionalized ILs. The anions of which actually were replaced by the anions of the electrolytes in which the monomers were dissolved. The RTILs used for the electropolymerization thus determined the electrochemical behavior of the monomers, surface morphologies and the physicochemical properties of the poly(ILs) films. After the modification of ITO electrodes with poly(ILs), the electrochemical performance of the semiconducting electrodes was significantly improved towards uric acid oxidation. The poly(ILs) show adjustable properties (via changing counter anions), and exhibit a wide range of solubility in organic solvents, and electrochromic and solvatochromic properties. The second report (shown in chapter 3) is focused on mono- and di-carbazole functionalized viologen compounds, which were characterized using 1H, 13C, 19F NMR, and ESI-MS. Suitable cyclic voltammetric techniques were developed to polymerize these compounds on the ITO and glassy carbon (GC) electrode through a radical-induced polymerization triggered by electrochemical oxidation of carbazole moieties in electrolytes composed of NaClO4/acetonitrile or room temperature ionic liquid/organic solvents (acetonitrile, propylene carbonate). The basic physical properties and reactivity of these polymers were studied. It was found that the properties of the electropolymerized polymers were crucially controlled by the chemical structure of the monomer and the electrolyte compositions. The polymer films showed electrochromic behavior, and the color changed from greenish at the potential where carbazole groups were oxidized to violet or colorless at which reduction of viologen groups occurred; violet or colorless depended on which of the two reductive states of the viologen moieties was reached. The polymer films were capable of enhancing the oxidative current of uric acid and ascorbic acid, respectively, in neutral media, which might be due to the concentrating ability of the viologen moieties towards negatively charged species such as ferricyanide ([Fe(CN)6]3−) and ferrocyanide ([Fe(CN)6]2−). The third report (shown in chapter 4) is focused on study of di-carbazole functionalized viologen compounds, cyclic voltammetric techniques were developed to polymerize these compounds on glassy carbon (GC) electrode through a radical-induced polymerization by electrochemical oxidation of carbazole moieties in electrolytes composed of room temperature ionic liquid/organic solvents (propylene carbonate). It was found that the properties of the electropolymerized polymers can be enhanced by chemically fabricating metal nano particles on surface of the polymer by adsorption or deposition. The modified polymer electrode enhances the rate of electro chemical oxidation reaction. In summary, my PhD program mainly contributes to develop a new type of ionic liquids and ionic compounds. Different polymerization techniques have been developed to polymerize these compounds on electrode surface using ionic liquids and organic solvents. These compounds were characterized and their physical properties were studied. The results from these studies have allowed us to develop interesting application such as sensors, electrochromism and solvatochromism. In future will help us to broaden their application towards energy storage application.
參考文獻
延伸閱讀
- 林逸鈞（2022）。以紫外光固化電解質及原位聚合法製備電致色變元件及其性質研究〔碩士論文，淡江大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0002-2208202219331900
- 吳昇璜（2015）。聚合型離子液體修飾電極於電化學分析的開發〔碩士論文，國立中正大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0033-2110201614033165
- 李子念（2013）。應用於離子感應場效電晶體之自主裝單分子層/氧化層堆疊感測薄膜研究〔碩士論文，國立暨南國際大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0020-1308201321233000
- Yang, D. (2008). Development of polymers for electroplating waste water purification, polymer-supported reagents for organic synthesis and heterogeneouscatalysts for aerobic alcohol oxidation reactions [master's thesis, The University of Hong Kong]. Airiti Library. https://www.airitilibrary.com/Article/Detail?DocID=U0029-1812201200012539
- Chung, C. H. (2007). Synthesis, Stable Electrochemical and ElectrochromicProperties of New Aromatic Polymers Bearing Pendent Triphenylamine Groups [master's thesis, National Chi Nan University]. Airiti Library. https://www.airitilibrary.com/Article/Detail?DocID=U0020-1408200715502700