二氧化鈦、二氧化鈰/聚苯胺核－殼奈米複合材料之研究

Studies on TiO2, CeO2/polyaniline core-shell nanocomposites

莊豐憶(Feng-Yi Chuang)

指導教授 ： 楊思明

國立中央大學/工學院/化學工程與材料工程學系/博士(2008年)

摘要

本論文主要分成三部分：第一部分為先以矽烷偶合劑修飾二氧化鈦奈米粒子的表面，使得二氧化鈦粒子的表面上帶有胺基或苯環基，而後加入苯胺單體鹽酸鹽離子，並且加入過硫酸銨氧化劑開始起始聚合反應，形成二氧化鈦/聚苯胺核－殼奈米複合材料。然而，由於苯胺單體鹽酸鹽離子能夠溶解於水溶液中，因此不僅在二氧化鈦粒子的表面上會有聚苯胺的產生，溶液中亦會有單獨存在的聚苯胺高分子；所以必須以能溶解聚苯胺的溶劑(NMP)來移除單獨存在的聚苯胺鏈，而僅留下全為核－殼結構的二氧化鈦/聚苯胺奈米複合材料。
第二部分為以二氧化鈰奈米粒子為核，並且在不額外添加氧化劑的狀況下，直接以二氧化鈰當作氧化劑，將苯胺單體鹽酸鹽離子聚合在二氧化鈰粒子的表面上，形成二氧化鈰/聚苯胺核－殼奈米複合材料。此時二氧化鈰表面上的Ce4+被還原形成Ce3+。然而由於二氧化鈰粒子為鹼性氧化物，因此只有在適當的鹽酸濃度下才會形成核－殼結構的奈米複合材料。
第三部分為同樣以二氧化鈰奈米粒子為核，但是預先以十二烷基苯磺酸將二氧化鈰粒子分散於水溶液中，而後再將苯胺單體鹽酸鹽離子聚合在二氧化鈰粒子的表面上，形成二氧化鈰/聚苯胺核－殼複合材料。然而由於在以十二烷基苯磺酸分散二氧化鈰粒子時，二氧化鈰的粒子形狀已變成三角形，因此所聚合形成的二氧化鈰/聚苯胺核－殼複合材料亦為三角形。另一方面，若先以polyvinylpyrrolidone分散二氧化鈰粒子，然後再依照上述步驟形成核－殼複合材料，則可以使複合材料的粒徑變小。

關鍵字

二氧化鈦 ； 二氧化鈰 ； 聚苯胺 ； 核-殼奈米複合材料

並列摘要

There are three parts in this thesis. In the first part, the surface of titanium dioxide nanoparticles were modified by silane, introducing amine groups or phenyl amine groups bounded on the surface of titanium dioxide nanoparticles. Then, aniline can be polymerized with amine (or phenyl amine groups) of silane to form the titanium dioxide/polyaniline core-shell nanocomposites using ammonium persulfate as oxidant. However, anilinium ions were polymerized not only on the surface of titanium dioxide nanoparticles but also in the solution. Thus, it’s necessary to use N-Methyl-2-Pyrrolidone (NMP) to remove polyaniline not bonded to titanium dioxide core.
In the second part, cerium dioxide nanoparticles were used as core and oxidant at the same time, anilinium ions were polymerized on the surface of cerium dioxide nanoparticles and form cerium dioxide/ polyaniline core-shell nanocomposites. Herein, Ce4+ on the surface of cerium dioxide nanoparticles was reduced to Ce3+. However, the core-shell nanocomposites can only be formed when the concentration of hydrochloric acid was lower due to the alkaline character of cerium dioxide.
In the third part, cerium dioxide nanoparticles were also used as the core, but dodecylbenzenesulfonic acid (DBSA) solution was used to disperse cerium dioxide nanoparticles in advance. Then, anilinium ions were polymerized on the surface of cerium dioxide particles to form triangular cerium dioxide/polyaniline core-shell composites. However, when the cerium dioxide nanoparticles were dispersed in DBSA solution, the morphology of cerium dioxide particles becomes triangular already. Thus, triangular cerium dioxide/polyaniline core-shell composites were formed after polymerization of polyaniline on the surface of triangular cerium dioxide particles. On the other hand, if the cerium dioxides nanoparticles were dispersed by polyvinylpyrrolidone (PVP) before DBSA was added, triangular cerium dioxide/polyaniline core-shell composites of smaller size were obtained.

並列關鍵字

TiO2 ； Polyaniline ； CeO2 ； Core-shell nanocomposites

參考文獻

[2] D. C. Trivedi, S. K. Dhawan, Synth. Met. 59 (1993) 267.

(2003) 255.

[11] R. Gangopadhyay, A. De, Chem. Mater. 12 (2000) 608.

[12] S. Maeda, S. P. Armes, J. Colloid Interface Sci. 159 (1993) 257.

[13] S. Maeda, S. P. Armes, J. Mater. Chem. 4 (1994) 935.