臺灣博碩士論文加值系統

根據之前的研究發現碳纖維紙經由不同金屬奈米粒子修飾能對於許多物質有良好的催化性質，為了提升碳纖維紙的催化效果，在此研究中，利用電沉積奈米鈀的方式修飾電極改善電化學特性，加上對於此方法的條件優化並發揮催化特性感測特定物質或是參與其它反應。其中會使用循環伏安法探討電極對於過氧化氫的催化反應及其特性，氧化反應為33.26 μA。以及對於乙醇在鹼性環境中的氧化反應，催化反應峰值達到81.2 mA (541.32 mA cm-2) (68.22 mA mg-1 Pd)。並發現奈米鈀顆粒大小與分布對於不同物質的催化效果也會有影響。經由對於碳纖維紙電極的一系列標準化修飾，期望能將其應用在生物感測器或是燃料電池上。

According to the previous studies, the modification of carbon fiber paper (CFP) electrode with different metal nanoparticles demonstrates great catalytic properties toward many bioactive molecules. In this study, in order to promote the catalytic abilities of CFP, the electrodeposition of palladium nanoparticles (Pd NPs) has adopted to improve the electrochemical characteristics on the surface of CFP. The Pd-based CFP electrodes are optimized to sense or react with specified molecules. The catalytic reaction of hydrogen peroxide is explored by cyclic voltammetry (CV) and the oxidative current is 33.26 μA. In addition, the oxidation reaction of ethanol in alkaline media is also demonstrated by CV. PdNP/CFP electrode exhibits a peak current and current density of 81.2 mA and 541.32 mA cm-2 (or 68.22 mA mg-1 Pd), respectively. Moreover, the morphologies and distribution of Pd NPs on CFP are the factors to affect the catalytic properties. Through the optimal modification on the surface of CFP, we expect it could be applied in the development of biosensor and fuel cell.

Content
中文摘要 i
Abstract ii
Acknowledgement iii
Content iv
Content of Figures and Tables vi
1. Introduction 1
1-1 Carbon fiber paper as electrocatalyst support 1
1-2 Properties and application of palladium nanoparticles 1
1-3 Electrochemical biosensor 2
1-4 Direct ethanol fuel cell 3
1-4.1 Alternative fuels 3
1-4.2 Direct ethanol fuel cell 4
1-5 Motivation and purpose 5
2. Materials and Methods 7
2-1 Materials 7
2-2 Apparatus 7
2-3 Oxygen plasma treats working electrode 7
2-4 Electrodepositing palladium on the surface of carbon fiber paper electrode 7
2-5 Electrode preparation 8
2-6 Electrochemical Analysis 8
3. Results and Discussion 9
3-1 The preparation of palladium nanoparticle-deposited electrode for biosensor 9
3-1.1 The pretreatment of the electrode and electrodeposition of Pd nanoparticles
on the CFP surface 9
3-1.2 Optimization of PdNP-electrodeposited CFP electrode for redox reaction of
H2O2 9
3-2 Characterization of PdNP/CFP for biosensor 11
3-2.1 Scanning electron microscopy and energy dispersive X-ray spectrometry
(EDS) analysis of palladium nanoparticles on CFP electrodes 11
3-2.2 Thermogravimetric analysis of PdNP/CFP electrodes 11
3-3 Electrochemical response of PdNP/CFP electrodes to H2O2 12
3-4 The preparation of palladium nanoparticle-deposited electrode for fuel cell 14
3-4.1 The pretreatment of the electrode and electrodeposition of Pd nanoparticles
　 on the CFP surface 14
3-4.2 Optimization of PdNP-electrodeposited CFP electrode for redox reaction of
fuel cell 14
3.5 Characterization of PdNP/CFP for fuel cell 16
3-5.1 Scanning electron microscopy and energy dispersive X-ray spectrometry
(EDS) analysis of palladium nanoparticles on CFP electrodes 16
3-5.2 Thermogravimetric analysis of PdNP/CFP electrodes 16
3-6 Electrochemical behavior of PdNP/CFP for fuel cell 16
3-6.1 Electrochemical behavior of PdNP/CFP in 1M KOH 16
3-6.2 Electrooxidation of ethanol on the PdNP/CFP electrodes 17
4. Conclusions 21
5. Future Work 22
6. References 23

Content of Figures and Tables
Figure 1. The cyclic voltammograms of CFP with or without plasma treatment in potassium phosphate buffer 32
Figure 2. Electrodeposition of palladium on the CFP electrodes 33
Figure 3. Electrochemical response of PdNP/CFP electrodes to hydrogen peroxide 34
Figure 4-A. Optimization of the electrodeposition conditions for Pd on CFP with the electrochemical response of H2O2 for biosensor: Effect of K2PdCl4 concentrations 35
Figure 4-B. Optimization of the electrodeposition conditions for Pd on CFP with the electrochemical response of H2O2 for biosensor: Effect of scanning cycles of CV 37
Figure 4-C. Optimization of the electrodeposition conditions for Pd on CFP with the electrochemical response of H2O2 for biosensor: Effect of scan rates of CV 39
Figure 4-D. Optimization of the electrodeposition conditions for Pd on CFP with the electrochemical response of H2O2 for biosensor: pH values of electroplating solution 41
Figure 5. Scanning electron microscopic images of CFP electrodes with or without plasma treatment 43
Figure 6. Scanning electron microscopic images and energy dispersive X-ray spectrometry of PdNP/CFP electrodes 44
Figure 7. Thermogravimetric analysis of PdNP/CFP electrodes in air 45
Figure 8. Electrochemical response of PdNP/CFP electrodes in potassium phosphate buffer 46
Figure 9. Electrochemical response of PdNP/CFP electrodes to hydrogen peroxide after optimized by protocol A 47
Figure 10. The effect of different pH value potassium phosphate buffer to H2O2 48
Figure 11. Scanning electron microscopic images of PdNP/CFP electrodes and electrochemical response to hydrogen peroxide and ethanol: 2 cycles 49
Figure 12. Scanning electron microscopic images of PdNP/CFP electrodes and electrochemical response to hydrogen peroxide and ethanol: 5 cycles 51
Figure 13. Scanning electron microscopic images of PdNP/CFP electrodes and electrochemical response to hydrogen peroxide and ethanol: 10 cycles 53
Figure 14. Scanning electron microscopic images of PdNP/CFP electrodes and electrochemical response to hydrogen peroxide and ethanol: 20 cycles 55
Figure 15. Scanning electron microscopic images of PdNP/CFP electrodes and electrochemical response to hydrogen peroxide and ethanol: 40 cycles 57
Figure 16. The cyclic voltammograms of ethanol oxidation reaction 59
Figure 17-A. Optimization of the electrodeposition conditions for PdNP on CFP with the electrochemical response of ethanol oxidation for fuel cell: Scan rates of CV 60
Figure 17-B. Optimization of the electrodeposition conditions for PdNP on CFP with the electrochemical response of ethanol oxidation for fuel cell: Scanning cycles of CV 62
Figure 18. Scanning electron microscopic images and energy dispersive X-ray spectrometry of PdNP/CFP electrodes 64
Figure 19. Thermogravimetric analysis of PdNP/CFP electrodes in air 65
Figure 20. Electrochemical behavior of PdNP/CFP electrodes to 1 M KOH 66
Figure 21. CV curves of PdNP/CFP electrodes in 1 M KOH with 1 M ethanol 67
Figure 22. The effect of different potential range to the oxidation of ethanol 68
Figure 23. Chronoamperometric curve of PdNP/CFP electrodes for ethanol oxidation at different potentials 69
Figure 24. The influence of acetaldehyde to ethanol oxidation in 1M KOH 70
Table 1. Energy density and price per kWh of different fuels 71
Table 2. The comparison of the performance of Pd-based carbon electrodes for ethanol oxidation in alkaline media 72

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