臺灣博碩士論文加值系統

Since bimetallic nanomaterial was credited with far features beyond single metal nanomaterial and has shown much outstanding performances in such fields, energy, biosensors, imaging, it has attracted much attention in nanotechnology recently. The improvement of oxygen reduction reaction (ORR), the cathodic reaction in renewable energy technologies, such as fuel cells, metal-air batteries, and so forth, is of vital importance due to the increasing demands of energy by rising steeply population. The ORR commonly involves four-electron (4e-) transfer to produce water directly, whereas another parallel two-electron (2e-) pathway producing undesired and damaging peroxide species competes against the initial 4e- pathway. Based on above-mentioned conditions, we were about to develop the bimetallic nanomaterial with surface character of surface plasmon resonance to alter the ORR pathways toward 4e- pathway.
Herein, we demonstrated the first empirical evidence of tunable two-/four-electron pathway toward ORR through plasmonic effects (up to 0.2 mA/cm2 enhancement in current density and 4% pathway alternation to 4e-), in which plasmonic Ag-Pt bimetallic nanocages were synthesized with an edgeless feature and a custom-made RDE/RRDE working station was designed to provide unique means by which to realize the plasmonic effects toward the target oxygen reduction reaction. The edgeless Ag-Pt bimetallic nanocages with hollow interior performed newly plasmonic induced effects to alter the reaction pathway of ORR, where the formation of undesired peroxide intermediate was significantly suppressed since the hot electron transfer of Ag nanostructure offered sufficient energy to populate the antibonding orbital of O2. This rapid light-dependent nature corresponding to localized surface plasmon resonance can potentially offer synergetic strategies toward altering the chemical reactions or reaction pathways in various fields.

目錄
目 錄…………………………………………………………………………….....….I
圖目錄…………………………………………………...…………………………..…IV
表目錄………………………………………………………..……………...…………IX

第一章 緒論 1
1.1奈米材料 1
1.1.1小尺寸效應 1
1.1.2表面效應 1
1.1.3量子尺寸效應 2
1.1.4奈米材料於化學催化應用 3
1.1.5奈米材料製備方法 4
1.2表面電漿共振 (Surface Plasmon Resonance; SPR) 7
1.2.1侷限表面電漿共振 (Localized Surface Plasmon Resonance; LSPR) 8
1.2.2銀之表面電漿共振表現 13
1.3氧氣還原反應 (Oxygen Reduction Reaction; ORR) 16
1.3.1反應路徑 16
1.3.2電化學表現 18
1.3.3金屬催化劑於氧氣還原反應 19
1.4本研究目的 21
第二章 實驗步驟與儀器分析原理 22
2.1本研究實驗流程 22
2.2化學藥品 23
2.3雙金屬奈米材料製備 24
2.3.1奈米銀立方 (silver nanocube) 24
2.3.2雙金屬銀鉑奈米材料合成 (AgPt bimetallic nanomaterial) 25
2.4樣品鑑定與分析 26
2.4.1紫外-可見光譜分析儀 (Ultraviolet-visible spectrometer) 27
2.4.2電子顯微鏡 (Electron Microscopy; EM) 29
2.4.3感應耦合電漿質譜分析儀 34
(Inductively Coupled Plasma-Mass Spectrometer; ICP-MS)
2.4.4同步輻射光源 (Synchrotron Radiation) 35
2.5電化學分析 40
2.5.1電化學架設 40
2.5.2循環伏安法 (Cyclic Voltammetry; CV) 45
2.5.3線性掃描伏安法 (Linear Sweeping Voltammetry; LSV) 46
2.5.4定電位測定法 (amperometric i-t curve; i-t) 47
2.6時域有效差分法 (Finite-Difference Time-Domain; FDTD) 48
第三章 結果與討論 49
3.1奈米銀立方製備—還原劑效應 49
3.1.1紫外-可見光譜分析儀分析 50
3.1.2電子顯微鏡分析 52
3.2銀鉑雙金屬奈米材料 55
3.2.1紫外-可見光譜分析 56
3.2.2電子顯微鏡分析 58
3.2.3感應耦合電漿質譜分析 61
3.3氧氣還原反應之催化活性探討 62
3.3.1氮氣環境下之氧氣還原反應性 62
3.3.2氧氣環境下之氧氣還原反應性 65
3.3.3光照對於氧氣還原反應路徑影響 70
3.3.4單波長雷射對所製備樣品—AgPt-30之氧氣還原反應影響 78
3.4反應路徑改變機制探討 80
3.4.1加熱於氧氣還原反應影響 81
3.4.2臨場X-ray吸收光譜測量 86
3.4.3時域有效差分法模擬 88
3.4.4反應路徑改變機制 90
第四章 結論 94

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