臺灣博碩士論文加值系統

本研究主要在探討二氧化碳在四種不同表面修飾之透明導電玻璃電極與含有三種不同過渡金屬(鈷、鐵、鎳)-亞硝基錯合物之電解質的電解系統之還原行為。藉由將二氧化碳以電化學催化的方式還原成甲醇，不僅能減少在大氣中過多的氧化碳，還能解決能源短缺的問題。
四種電極包括FTO透明導電電極、普魯士藍修飾之FTO透明導電電極(FTO|PB)、白金修飾之FTO透明導電電極(FTO|Pt)以及普魯士藍修飾之FTO|Pt透明導電電極(FTO|Pt|PB)。普魯士藍之角色為電子傳遞媒介而過渡金屬(鈷、鐵、鎳)-亞硝基錯合物則為催化二氧化碳還原之電觸媒。研究結果發現，含有鈷-亞硝基錯合物之電解系統對二氧化碳還原催化活性最佳，二氧化碳在四種電極上皆可生成甲醇，其中二氧化碳在FTO|Pt|PB轉換成甲醇的法拉第效率最高接近52.83 ± 17.10%。而含有亞鐵-亞硝基錯合物之電解系統活性次之，二氧化碳還原生成甲醇之發拉第效率最高可達11.50 ± 12.14%。最後，在含有鎳-亞硝基錯合物的電解系統對於二氧化碳的還原幾乎無催化作用。這些結果與1980年代Ogura團隊的結果不甚相同。他們使用Pt|PB工作電極催化二氧化碳還原並在亞鐵-亞硝基錯合物中得到83%左右的甲醇轉化法拉第效率。相較於含有鈷-亞硝基錯合物，亞鐵-亞硝基錯合物與鎳-亞硝基錯合物的甲醇轉化法拉第效率較低的原係因為在溶液中的錯合物穩定性較低，影響催化活性，或者其他副產物的產生，但礙於氣相層析儀的管柱的靈敏度，在此研究中無法進行分析與定量。

In this study, the electrochemical reduction of CO2 using the electrocatalytic systems, which consists of four types of surface-modified fluorine-doped tin oxide coated glass electrodes (FTO) and three kinds of transition metal (Co2+, Ni2+, Fe2+) nitroso–R complexes was investigated. By reducing the CO2 into methanol, it can not only eliminate the excess emission of CO2 in atmosphere but also generate an alternative energy to solve both severe greenhouse effect and the energy crisis.
The four types of surface-modified FTO electrodes include bare FTO, Prussian blue modified FTO (FTO|PB), Platinum (Pt) modified FTO (FTO|Pt), and Prussian blue modified FTO|Pt (FTO|Pt|PB) electrodes. The PB thin film, prepared by electrodeposition, acts as the electron transfer mediator in this work, whereas the transition metal nitroso-R complexes was used as the electrocatalysts electrocatalyzing the electrochemical reduction of CO2. It was found that the electrocatalytic system containing cobalt nitroso-R complex showed best electrocatalytic activity towards the reduction of CO2; methanol production was noticed for all the four types of electrodes, and the maximal Faradaic efficiency of 52.83 ± 17.10% can be achieved using FTO|Pt|PB. The electrocatalyst system containing ferrous nitroso-R complex exhibited second best activity; the maximal Faradaic efficiency of 11.50 ± 12.14% can be achieved using FTO|Pt|PB. The electrocatalyst system containing nickel nitroso-R complex didn’t exhibit any activity towards the electrochemical reduction of CO2 into methanol.
These results is quite different from the previous work done by Ogura group in 1980s, in which they employ Pt|PB as the working electrode and ferrous nitroso-R complex showed the best activity to methanol production with a Faradaic efficiency of 83%. The lower or ignorable activity of electrocatalytic systems containing ferrous nitroso-R complex and nickel nitroso-R complex could be attributed to the fact that the instability of these two complexes under cathodic conditions or other byproducts, which cannot be detected and quantified using gas chromatography, formed during the electrochemical reduction of CO2.

中文摘要 I
Abstract II
Acknowledgement IV
Table of Content V
List of Tables VIII
List of Figures IX
Chapter 1 INTRODUCTION 1
1.1 General information 1
1.2 Schemes for dealing with CO2 2
1.2.1 Carbon capture and separation 3
1.2.1.1 Carbon capture 3
1.2.1.2 Carbon separation 6
1.2.2 Carbon transportation and storage 8
1.2.3 Carbon recycle into fuel 11
1.2.3.1 Thermochemical conversion of CO2 13
1.2.3.2 Electrochemical conversion of CO2 15
1.2.3.2.1 Effects of ionic liquid on the electrochemical reduction of CO2 16
1.2.3.3 Photoelectrochemical conversion of CO2 17
1.2.4 Electrocatalysts for the electrochemical reduction of CO2 23
1.2.4.1 KOH/HF treated metallic Molybdenum 23
1.2.4.2 Pyridine 24
1.2.4.3 Prussian blue/metal complex electrocatalytic system 25
1.3 Motivation 27
Chapter 2 EXPERIMENTAL SECTION 28
2.1 Materials 28
2.2 Instrumentation 30
2.3 Material synthesis 32
2.3.1 Electrode preparation 32
2.4 Physical characterization 35
2.4.1 Scanning electron microscopy (SEM) 35
2.4.2 Raman spectroscopy 35
2.4.3 Inductively coupled plasma-mass spectroscopy (ICP) 36
2.4.4 Ultraviolet-visible spectroscopy (UV-vis) 36
2.4.5 Gas Chromatography 39
2.5 Electrochemical characterization 42
Chapter 3 RESULTS AND DISCUSSION 45
3.1 Physical characterization on the PB modified electrodes 45
3.2 Electrochemical properties of transition metal complexes 47
3.2.1 Redox behavior of cobalt nitroso-R complex (Co-NRS) on FTO 47
3.2.2 Redox behavior of Nickel (II) nitroso-R complex (Ni-NRS) 57
3.2.3 Redox behavior of ferrous nitroso-R complex (Fe-NRS) 59
3.2.4 Product analyses for CO2 reduction using Ni-NRS and Fe-NRS 61
Chapter 4 CONCLUSION AND SUGGESTION 64
4.1 Conclusion 64
4.2 Suggestion and Outlook 66
4.2.1 Activity of NRS over different electrode 66
4.2.2 Immobilization of transition metal complex 67
4.2.3 Substrate effect 67
Reference 69
Appendix 77

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