臺灣博碩士論文加值系統

有機/無機複合材料在室溫下對氨氣的傳感性能備受關注，本研究使用硝酸鈰前驅溶液與靜電紡絲(Electrospinning)技術製備奈米纖維，透過高溫鍛燒形成二氧化鈰(CeO2)中空奈米纖維結構，經X光繞射儀(X-ray diffractometer, XRD)、掃描式電子顯微鏡(Field-emission scanning electron microscope, FE-SEM)、穿透式電子顯微鏡(Transmission electron microscope, TEM)等分析確認CeO2晶體以及中空纖維形貌形成。
接著以原位聚合法合成聚苯胺(Polyaniline, PANI)並添加不同比例之二氧化鈰中空纖維形成聚苯胺/二氧化鈰(PANI/CeO2)複合材料，同樣進行XRD、SEM、TEM等材料分析觀察表面形貌以及化學結構及晶體結構，並探討CeO2中空纖維添加量對聚苯胺披覆形貌以及室溫下氨氣檢測之影響，結果顯示添加20 wt%之CeO2纖維時形成最均勻之披覆，在1 ppm氨氣濃度下有最高之氣體響應值20.82。
接著利用高壓水熱法製備摻氮石墨烯量子點，並與CeO2中空纖維以靜電吸引的方式產生吸附，藉由兩者界面電位、TEM進一步證實，最後將聚苯胺進行披覆以形成聚苯胺/摻氮石墨烯量子點-二氧化鈰(PANI/NGQD-CeO2)三元複合材料，觀察到碳材加入後響應值提升至24.68，並對其進行氨氣之重複性、選擇性、長期穩定性之氣敏性能檢測。

The sensing performance of organic/inorganic composite materials for ammonia gas sensors at room temperature has garnered significant attention. In this study, a cerium nitrate precursor solution was utilized along with electrospinning technology to fabricate the nanofibers. These nanofibers were then subjected to high-temperature calcination to yield a hollow cerium dioxide (CeO2) nanofiber with crystalline structure. Analysis conducted via X-ray diffractometer (XRD), Field-emission scanning electron microscope (FE-SEM), and Transmission electron microscope (TEM) confirmed the formation of CeO2 crystals with hollow morphology.
Following that, aniline monomer and different ratios of cerium dioxide hollow fibers were mixed and synthesized using an in-situ polymerization method to form polyaniline/cerium dioxide (PANI/CeO2) composite materials. Similarly, XRD, SEM, and TEM were employed to observe surface morphology, chemical structure, and crystal structure. Furthermore, the effect of the additional CeO2 on the morphology of polyaniline of composite materials and the detection of ammonia gas at room temperature was investigated. The results indicate that the addition of 20 wt% CeO2 forms the most uniform coating thickness with the highest gas response value of 20.82 at a 1 ppm ammonia gas concentration.
Next, N-doped graphene quantum dots (NGQD) prepared using a hydrothermal method were adsorbed onto the CeO2 hollow fibers through electrostatic attraction. This process was further confirmed by Zeta potential analysis and TEM. Finally, polyaniline was coated to form a PANI/NGQD-CeO2 ternary composite material. It was observed that the addition of carbon material increased the response value to 24.68. The sensing performances in terms of repeatability, selectivity, and long-term stability of ammonia gas were also evaluated.

摘要 i
Abstract ii
目錄 iv
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 3
1.3 研究目的與方向 4
第二章 文獻回顧與基本理論 6
2.1 基本能帶理論 6
2.1.1 p型與n型半導體 8
2.1.2 p-n接面(p-n junction) 9
2.2 氣體感測器 10
2.2.1 導電高分子(Conductive polymer) 12
2.2.2 金屬氧化物(Metal oxide, MOx) 14
2.2.3 氣體感測機制 16
2.3 靜電紡絲 17
2.4 聚苯胺(Polyaniline, PANI) 20
2.4.1 聚苯胺之製備 23
2.5 二氧化鈰(Cerium oxide, CeO2) 25
2.5.1 二氧化鈰之製備 27
2.6 摻氮石墨烯量子點(N-doped graphene quantum dots, NGQD) 32
2.6.1 摻氮石墨烯量子點之製備 35
2.7 氨氣感測之研究 38
2.7.1 聚苯胺/碳材複合材料 38
2.7.2 聚苯胺/金屬氧化物複合材料 40
2.7.3 導電高分子/碳材/金屬氧化物複合材料 43
第三章 實驗方法與步驟 45
3.1 實驗材料 45
3.2 實驗儀器 47
3.3 實驗架構 49
3.4 實驗步驟 50
3.4.1 二氧化鈰中空奈米纖維之製備 50
3.4.2 聚苯胺/二氧化鈰複合材料之製備 53
3.4.3 摻氮石墨烯量子點之製備 55
3.4.4 聚苯胺/摻氮石墨烯量子點吸附二氧化鈰纖維之製備 56
3.4.5 氣體感測實驗 58
3.5 實驗儀器分析 60
3.5.1 X光繞射儀 (X-ray diffractometer, XRD) 60
3.5.2 傅立葉轉換紅外線光譜儀(Fourier transform infrared spectrometer, FTIR) 60
3.5.3 化學分析電子能譜儀(Electron spectroscope for chemical analysis, ESCA) 61
3.5.4 場發射掃描式電子顯微鏡(Field-emission scanning electron microscopy, FESEM) 61
3.5.5 紫外/可見光分光光譜儀 (Ultraviolet-visible spectrophotometer, UV-Vis) 62
3.5.6 穿透式電子顯微鏡 (Transmission electron microscope, TEM) 62
3.5.7 界面電位分析儀 (Zeta potential analyzer) 63
3.5.8 拉曼光譜儀 (Raman spectrometer) 63
3.5.9 高效能氣體吸附比表面積及孔徑分析儀(Gas sorption analyzer) 63
3.5.10 原子力顯微鏡(Atomic force microscopy, AFM) 64
第四章 結果與討論 65
4.1 二氧化鈰奈米中空纖維之性質分析 65
4.2 聚苯胺/二氧化鈰複合材料 71
4.2.1 聚苯胺/二氧化鈰複合材料之材料性質分析 71
4.2.2 聚苯胺/二氧化鈰複合材料之氨氣感測 78
4.3 摻氮石墨烯量子點之基本性質分析 83
4.3.1 摻氮石墨烯量子點吸附二氧化鈰基本性質分析 87
4.4 摻氮石墨烯量子點吸附二氧化鈰/聚苯胺三元複合材料 91
4.4.1 摻氮石墨烯量子點吸附二氧化鈰/聚苯胺三元複合材料之基本性質分析 91
4.4.2 摻氮石墨烯量子點吸附二氧化鈰/聚苯胺三元複合材料之氨氣感測 95
4.5 與相關文獻之比較 105
第五章 結論 106
第六章 參考文獻 108

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