本論文主要利用化學還原法，製備各式新穎p-type之Cu2O及CuO奈米結構、n-type之ZnO奈米結構、及其混合之p-n異質接面奈米結構，並探討此些奈米結構對光觸媒特性之影響。
在p-type之Cu2O及CuO奈米結構合成方面，Cu2O係利用典型Cu金屬奈米粒子製程於水中自然氧化所得，其形貌為圓球形，尺寸約為5 nm。其後再藉由各種氧化參數之改變，在液相水介質之中，將製備所得之零維Cu2O奈米粒子，轉變成為各式一維、二維之CuO奈米結構，包含鹿角狀、線形與片狀等等形貌，其長約100 ~350 nm，寬約15~120 nm不等。其中，並發現一維短柱狀Cu(OH)2奈米結構之存在，其長約數μm，寬約70 nm。
在n-type之ZnO奈米結構合成方面，藉由製程參數之調控，製備出一維單晶柱、八面體結構及三維花形結構。並利用懸浮零維Cu2O奈米粒子作為基材，使ZnO奈米結構直接成長於其上，合成出CuO/ZnO之 p-n 異質接面結構。實驗結果證實，透過ZnO與CuO的結合，可延長其受光激發電子與電洞的分離時間，使其光催化效果較單純混合ZnO與CuO奈米結構為佳，以線形CuO/花形ZnO複合材料為例，當使用Rhodamine B (Rh-B)作為染料時，其光催化效能可比直接混合兩材料提昇45%左右。在此些CuO/ZnO異質接面奈米結構中，以線形CuO/柱狀ZnO複合材料的光催化效果為最佳。
由於奈米粒子經常與其本身塊材之形貌有所不同，故本論文針對一些常見的奈米粒子形貌，進行XRD繞射光譜的理論模擬，在金屬奈米粒子方面包括球形、方形、十面體與二十面體奈米粒子，在氧化物方面則包含球形、方形與線形。從模擬數據與實驗數據的分析比對，歸納出由XRD繞射峰的強度比快速得知奈米粒子形貌之方法。

This thesis contains two main topics: heterojunction nano-structures and photocatalysts. First, a series of novel p-type Cu2O and CuO, n-tpye ZnO, and their mixed p-n heterojunction nano-structures were newly prepared mainly by chemical reduction method. Second, the nano-structures obtained were applied as photocatalysts and the nano-structural influence on photocatalytic performance was compared and discussed.
Cu2O was prepared by spontaneous oxidation of spherical Cu nano-particles (~5 nm in diameter) in water at room temperature. Several novel CuO nano-structures were then simply synthesized by the further oxidation of the prepared Cu2O nano-particles in aqueous solutions. Accompanying with the oxidation process, a distinct morphological transformations from zero-dimensional (Cu2O) to one-dimensional or two-dimensional (CuO) was found and its mechanism is considered as the key point to produce such a variety of CuO nanostructures including buckhorn-like rods, short rods, and flakes, in this work. In addition, one-dimensional Cu(OH)2 nano-structures (~100 nm long and 15 nm in width) can also be found under some oxidation conditions.
ZnO nano-structures including one-dimensional single crystal rods, octahedra and three-dimensional flower-like assemblies were synthesized. In addition, using suspended Cu2O nano-particles as substrates, ZnO nano-structures could directly grow on Cu2O to form a p-n heterojunction ZnO/CuO composite. Our photocatalytic experiment has proved that the p-n heterojunction ZnO/CuO composite prepared indeed presents at least 45% enhancement of the degradation efficiency of organic dye, Rhodamine B, comparing with the simple mixture of CuO and ZnO nano-structures.
Nano-structures generally demonstrate a variety of morphologies in comparison with bulk materials. In this thesis, we illustrated a series of XRD analysis with theoretical calculations to distinguish some frequently observed morphologies of nano-particles, including cube, sphere, decahedron and icosahedron for metals and sphere, cube and rod for oxides.

摘要 i
Abstract iii
致謝 v
目錄 vi
圖目錄 viii
表目錄 xii
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 2
第二章 文獻回顧 3
2-1 奈米粒子性質 3
2-2 CuO奈米結構製備方法 4
2-2-1 化學合成法 4
2-2-2 物理合成法 5
2-3 CuO奈米結構之應用 7
2-3-1 催化觸媒 7
2-3-2 氣體感測 7
2-3-3 場發射元件 7
2-4 Cu、Cu2O、CuO、ZnO之結晶構造 9
2-4-1 Cu 9
2-4-2 Cu2O 9
2-4-3 CuO 10
2-4-4 ZnO 10
2-5 光催化反應 12
2-5-1 光催化反應原理 12
2-5-2 半導體光催化觸媒 12
2-5-3 Rhodamine B染料簡介 14
2-6 光催化性質改善方法 17
2-6-1 材料能隙調整 17
2-6-2 材料形貌控制 19
2-6-3 材料表面改質 19
第三章 實驗內容與方法 21
3-1 實驗設備 21
3-2 實驗藥品 22
3-3 實驗方法與步驟 22
3-3-1 Cu2O奈米粒子製備流程 23
3-3-2 CuO、Cu(OH)2奈米結構製備流程 24
3-3-3 ZnO 奈米結構製備流程 25
3-3-4 CuO/ZnO 奈米結構製備流程 26
3-3-5 光催化實驗流程 27
3-4 奈米結構之結構鑑定與光譜分析 28
3-4-1 X光繞射(XRD) 28
3-4-2 紫外光-可見光吸收光譜(UV-vis absorption spectra) 29
3-4-3 掃描式電子顯微鏡(SEM) 30
3-4-4 X-Ray能量散佈分析儀(EDS) 31
3-4-5 穿透式電子顯微鏡(TEM) 31
第四章 結果與討論 32
4-1 Cu2O 32
4-2 CuO 36
4-2-1 鹿角狀CuO 36
4-2-2 線形CuO (Type I) 38
4-2-3 短柱狀Cu(OH)2 40
4-2-4 水草狀Cu(OH)2/CuO 43
4-2-5 片狀CuO 45
4-2-6 線形CuO (Type II) 47
4-3 ZnO 51
4-3-1 八面體ZnO 53
4-3-2 花形ZnO 56
4-4 CuO/ZnO 57
4-4-1 線形CuO/柱狀ZnO 57
4-4-2 線形CuO/花形ZnO 60
4-5 光催化測試 62
第五章 結論 66
參考文獻 67
附錄一 理論XRD模擬計算 72
附錄二 Cu2O之理論XRD模擬數據 81
附錄三 CuO之理論XRD模擬數據 84

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