臺灣博碩士論文加值系統

我們利用還原合成系統，藉由穩定劑CMC（Carboxymethylcellulose）所形成的微胞，在水相中製備1D-nanoSe。在這研究報告中，我們藉由調控室溫中硒前驅物與還原劑反應的時間來製備出不同長短軸比值的一維硒奈米材料，平均直徑分佈約為20 nm左右而長短軸比值可從4.6±1.2到96.7±21.3。我們也對材料的成長過程感到好奇，其型態上的轉變是由反應初期的球形粒子轉變成圓柱形粒子，在反應的過程中我們發現其一維硒奈米材料除了形態上的改變外，其晶形也由反應初期的monoclinic轉變成trigonal的硒。在製備複合材料的部份，我們可分為兩部分，第一部份首先將製備好的1D-nanoSe作為模版，利用非等向性的修飾製備出特殊結構的複合材料，例如內層材料維持為硒，而外層材料可為二氧化矽或是二氧化鈦等材料，形成核層（Core-Shell）結構。也因為內層材料維持為硒，我們利用硒容易反應的特性，例如：昇高溫度或是加入還原劑將內層硒移除，形成中空的二氧化矽或是二氧化鈦奈米管柱；第二部份利用硒還原電位不高的特性，在核層結構上，使金離子和奈米硒發生氧化還原反應，將奈米金修飾於二氧化矽或是二氧化鈦的內部，也藉由實驗參數，例如：金離子的濃度、金離子與奈米硒反應的時間長短，來控制修飾於二氧化矽或是二氧化鈦內部的奈米金數量以及形成的位置。

We demonstrated a simple chemical method for preparing suspended Se nanorods within carboxymethylcellulose (CMC) aqueous solution. The shapes of thus prepared nano-Se can be either spherical or rod-like. In the first part of my thesis, we showed that the mean aspect ratios of the 1D-nanoSe can be controlled in such synthetic system by varying the reaction time between the selenium precursor and the reducing agent. The diameters of the 1D-nanoSe were ca. 20 nm and the mean aspect ratios of the particles were ranging from 4.6±1.2 to 96.7±21.3. The growth mechanism for the 1D-nanoSe was carefully characterized by both the Raman spectral and TEM evidences during the growth sequence. The conformation of the particles changed from spherical shape to nanorods. Also, their crystallinities were changing from monoclinic to trigonal. In the second part of my thesis, thus prepared 1D-nanoSe was further used as a “chemical template” either (i) to synthesize core-shell nanostructures via a lattice-oriented surface coating, or (ii) to selectively modify the Se surface at the Se/shell interface. For instance, a “nanofloat” containing Se nanorod as the inner core and silica (or titania) as the outer shell material was demonstrated to be synthesized following the lattice-oriented coating process. Since nanoSe was reactive and removable by means of several processes, such as raising solution temperature or the addition of reducing agent. Those resulted in the formation of either silica or titania hollow nanorod. We have also investigated the Se surface modification by a redox reaction between Se0 and Au3+ forming Au nanoparticles attached on the Se surface. We found ways to control the amount and the location of Au nanoparticles at the Se/shell interface region. They can be achieved by carefully control several parameters, such as the concentration of the gold ions and the time of the redox reaction.

總目錄
中文摘要 i
英文摘要 ii
總目錄 iii
圖目錄 v
第一章 序論 1
1.1奈米材料及其科學研究 1
1.2奈米合成與化學合成技術 9
1.3 研究動機與目標 12
第二章 一維硒奈米材料之合成 13
2.1合成策略 13
2.2合成步驟及材料檢測 15
2.3粒子長短軸比值之操控 23
2.4非等向性之生長機制及證據 30
第三章 硒奈米圓柱及其核層複合材料 35
3.1一維奈米硒修飾二氧化鈦之合成探討 37
3.1.1藥品與材料檢測 37
3.1.2 1D-nanoSe@MPTMS/TiO2結構物之製程 38
3.1.3 1D-nanoSe@MPTMS/TiO2特殊結構物之製程及成長 42
3.1.4 硒的移除及中空TiO2奈米管的製備 52
3.2一維奈米硒修飾二氧化矽之合成探討 54
3.2.1 1D-nanoSe@SiO2之製程及結構 54
3.2.2 硒的移除及中空Silica奈米管的製備 60
3.3 1D-nanoSe@M (M=SiO2,TiO2)與奈米金之複合材料 64
3.3.1奈米金於核心硒材的選擇性修飾 66
3.3.2奈米金生長過程之觀察及證據 73
3.4結論與未來展望 76
參考文獻 77

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