光增強甲醇氧化反應為近年來光－燃料電池的重要研究課題。先前技術對於光增強甲醇氧化反應觸媒的研究多聚焦於金屬－半導體複合材料。本研究提出利用三維金屬奈米樹枝晶叢林做為光電極，在可見光照射下增強甲醇氧化反應。此純金屬奈米結構同時具有觸媒及光觸媒之功效。
本論文使用氟離子輔助加凡尼取代反應 (Fluoride assisted galvanic replacement reaction)，於室溫條件下，在矽 (Si)基材上快速成長了三維的銀 (Ag)、鉑－銀 (Pt－Ag)、金 (Au) 等奈米樹枝晶叢林結構，同時研究其材料特性及光觸媒效果。在Ag及Pt－Ag奈米樹枝晶上，可見光輔助甲醇氧化反應得到初步的驗證。在Au奈米樹枝晶上，甲醇氧化電流在寬頻可見光照射下 (69 mW－cm－2；λ ＞ 400 nm) 提升了28 %。我們更進一步比較了不同波長入射光對於甲醇氧化電流增強效果之差異，並且引入局部表面電漿子共振 (Localized surface plasmon resonance) 模型解釋此隨波長改變的光增強現象。此外，本研究提出的低成本、快速且可室溫操作的矽基金屬奈米樹枝晶製造方法，也為未來製造大面積自站立三維金屬奈米結構提供了新的思維方向。

Photo-enhanced methanol oxidation reaction (PEMOR) is a crucial issue in the development of photo-fuel cells. In the study of catalysts for the PEMOR, efforts have been focused on metal-semiconductor composites in the prior arts. In this study, we utilized metal dendritic nanoforests (DNFs) as the photo-elecrodes to boost methanol oxidation reaction under irradiation. These pure metallic nanostructures can serve as catalysts and photo-catalysts simultaneously. Besides, a facile fluoride assisted galvanic replacement reaction was developed to prepare three-dimensional Ag, Pt－Ag, and Au DNFs under ambient conditions. The material characteristics and photo-enhancement toward methanol oxidation reaction were studied. In the Ag and Pt－Ag DNFs, visible- light enhanced methanol oxidation reaction was preliminarily verified. In the Au DNFs, the oxidation current of methanol was boosted by 28 % under broadband visible light illumination (69 mW－cm－2；λ ＞ 400 nm) . We further compared the photo- enhancements under various irradiation wavelengths. Localized surface plasmon resonance was introduced to explain the wavelength- dependent enhancement. Moreover, the cost-effective and facile process suitable for room-temperature preparation of Si-based metal DNFs provides a new direction for preparing large-scale free-standing metallic nanostructures.

摘要 i
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1 甲醇氧化與燃料電池－持續50年的觸媒研究焦點 1
1.2 光輔助甲醇氧化－發電並同時降解有害物的觀點 6
1.3 電漿子 (Plasmon) 增強觸媒反應－有別於半導體光觸媒反應的新機會 17
1.4 加凡尼 (Galvanic) 取代反應－快速、大面積、低成本的室溫製程 31
1.5 本研究目標－自站立金屬奈米結構直接應用於光－燃料電池電極 42
第二章 鉑－銀奈米樹枝晶叢林－初步驗證金屬奈米結構的可見光增強甲醇氧化能力 [158] 45
2.1 背景介紹 45
2.2 研究方法 46
2.3 結果與討論 51
2.4 小結 68
第三章 金奈米樹枝晶叢林－進一步探討表面電漿子共振增強甲醇氧化之機制 [187] 70
3.1 背景介紹 70
3.2 研究方法 71
3.3 結果與討論 74
3.4 小結 93
第四章 結論 94
參考文獻 95
附錄一 本論文相關國際期刊論文、專利發表及研究計畫 115
附錄二 作者個人簡歷 116

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