本研究透過PECVD電漿方法製備了兩種型態的氮摻雜石墨烯，透
過控制製程參數，調整電漿強度可控制石墨烯的缺陷量，在藉由不
同缺陷的石墨烯進行氮元素的摻雜，發現氮原子與碳原子的鍵結態
可以被缺陷位置影響進而加以控制。本研究透過不同位置的氮摻雜
石墨烯粉末應用到氧氣還原反應的催化以及生化檢測上，發現有著異
的表現，其中HPN-MQGs可以在氧氣還原反應上達到3.94的電子
轉移。而高品質石墨烯作為uric acid(UA), ascorbic acid(AA) and
dopamine (DA)的檢測上則可以將偵測極限降低至2.5μM。之後為了
避免石墨烯粉末再堆疊，製作了無黏著劑(binder-free)的奈米石墨烯壁
(Graphene-Nano-Wall, GNW)以及氮摻雜奈米石墨烯壁 (Nitrogen-
doped Graphene Nano-Wall, NGNW)將之應用在製作有機系超級電容
的電極，透過GNW與NGNW可以分別提升正極的上限電位到
1.5V以及將負極從-2.0V增加到-2.5V，在組成一非對稱電雙層電容
器可以在商用電解液1M 四乙基四氟硼酸/碳酸丙烯酯Tetraethyl
ammonium tetrafluoroborate (TEABF4)/propylene carbonate (PC)中達到
4V的高電位窗，並且能量密度為53 Wh/kg以及功率密8000W/kg，
經過10000次充放電測試後可以維持100%的電容維持率。

This research prepared two types of graphene sheet through microwave
plasma torch chemical vapor deposition method (MPT-CVD). We fine-
tuned the parameters of process and controlled strength of plasma to
manipulate the defects of graphene and found a correlation between
nitrogen configuration and defect density. The nitrogen plasma has been demonstrated to effectively dope N atoms onto graphene sheets. The distribution of the N-doping types can be tuned by control of the
graphene defect density and the nitrogen plasma power to generate
multiple functionalities of the resultant materials. The medium-quality graphene doped at a high-power nitrogen plasma exhibits the highest
electrocatalytic activity toward the oxygen reduction reaction (ORR) with
a mean electron-transfer number of 3.94 which is comparable to that of
platinum. The high-quality graphene doped at a low-power nitrogen
plasma shows the high activity and selectivity for simultaneously
detecting uric acid (UA), ascorbic acid (AA), and dopamine (DA) and
detecting limit is 2.5 μM due to the high content of the pyridinic-N
structure. We also produced the binder-free, vertically grown graphene-nano-walls (GNW) and nitrogen-doped graphene-nano-walls (NGNW) electrodes respectively provide good examples for extending the upper potential limit of a positive electrode of EDLCs from 0.1 V to 1.5 V (vs. Ag/AgNO3) as well as the lower potential limit of a negative electrode of EDLCs from -2.0 V to ca. -2.5 V in 1 M Tetraethyl ammonium tetrafluoroborate (TEABF4)/propylene carbonate (PC) compared to ACs. This newly designed asymmetric EDLC exhibits a cell voltage of 4 V, specific energy of 53 Wh kg-1 and specific power of 8 kW kg-1 and ca. 100% capacitance retention after 10,000 cycles charge-discharge.

中文摘要 ...1
ABSTRACT...2
誌謝...3
目錄...4
圖目錄...9
表目錄...15
第一章 緒論與研究背景介紹...16
第二章 文獻回顧與研究動機...18
2.1 石墨烯的製備...18
2.2 摻雜石墨烯...24
2.3 各類電漿源成長GNW...26
2.3.1 微波電漿...29
2.4 垂直成長石墨烯(VERTICAL ORIENTED GRAPHENE, VG)...30
2.5拉曼光譜 (RAMAN SPECTROSCOPY)石墨烯材料分析...36
2.6 石墨烯的應用研究...37
2.6.1石墨烯在氧氣還原催化應用...37
2.6.2 石墨烯應用於生物感測...40
2.6.3 石墨烯在超級電容儲能應用...42
2.7 電化學分析方法...48
2.8 研究動機...61
第三章 藥品、儀器與實驗方法...63
3.1實驗藥品...63
3.2 實驗設備...64
3.3 實驗方法...65
3.3.1 實驗裝置...65
3.3.2 石墨烯粉末與氮摻雜石墨烯粉末的合成...65
3.3.3 GNW AND NGNW的製備...66
3.3.4 材料分析...67
3.3.4 電化學量測與分析...67
第四章 氮摻雜石墨烯製作應用於觸媒和生物感測器...70
4.1 石墨稀層數與缺陷的控制...70
4.2氮摻雜石墨烯的控制與成長...76
4.3 氮摻雜石墨烯粉末在氧氣還原反應觸媒與多巴胺檢測的應用...79
第五章 氮摻雜奈米石墨烯壁應用於高電壓超級電容...89
5.1垂直成長奈米石墨烯壁(GNW)與氮摻雜奈米石墨烯壁(NGNW)材料鑑定...92
5.2 垂直成長BINDER-FREE GNW提升上限電位窗...96
5.3 高電壓超級電容驗證結果...98
第六章 總結與未來展望...101
第七章 參考文獻...103

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