本研究使用台灣工業技術研究院 (Industrial Technology Research Institute, ITRI) 所開發的微波電漿火炬 (Microwave plasma torch, MPT)，此設備是利用電漿增強化學氣相沉積法 (Plasma-enhanced chemical vapor deposition, PECVD) 製備石墨烯粉末 (graphene powder, GP)。在研究中可以藉由調整甲烷 (CH4) 與氬氣 (Ar) 的參數控制石墨烯的品質，而石墨烯粉末可以做為鉑分散之載體使用，促使電極擁有產氫與儲氫的催化能力。我們將碳紙塗佈石墨烯粉末作為工作電極，並分別使用鉑線與 Ag/AgCl 作為對電極與參考電極組成三極系統，而電解液為 0.5 M H2SO4，最後為了將鉑分散至工作電極上，我們利用循環伏安法 (CV) 達到摻雜效果，可以看到在極低的鉑含量情況下表現出不錯的產氫與儲氫的催化能力，並且具有 291 m2∙g−1 的電化學活性面積，跟不少文獻相比皆更高，推測是因為利用此方法分散上去的鉑為奈米級粒子。並且近一步使用 FMP(Focus microwave plasma) 利用氮氣電漿製備氮摻雜石墨烯，發現其擁有更好地產氫與儲氫的催化能力。最後將電化學活化後的樣品進一步使用 PCT(Pressure concentration temperature) 量測其氫氣儲存效果，並在量測結果發現在 2.33 wt% 下的 Pt/GP-Ar25 竟然優於商用 10 wt% Pt/C，發現其結果歸功於電化學活化後之奈米 Pt 粒子在樣品上的分散與石墨烯優異的物理吸附特
性。

This research used the Microwave Plasma Torch (MPT) developed by the Industrial Technology Research Institute (ITRI) in Taiwan, which uses a plasma-enhanced chemical vapor deposition (PECVD) method to prepare graphene powder (GP). In the research, the quality of graphene can be controlled by adjusting the parameters of methane (CH4) and argon (Ar), and graphene powder can be used as a carrier for platinum dispersion, so that the electrode has the catalytic ability for hydrogen evolution reaction (HER). The graphene-coated carbon paper was used as the working electrode, and the platinum wire was used as the counter electrode. In 0.5 M H2SO4 electrolyte, a three-pole system was formed with the Ag/AgCl reference electrode, and the Pt was dispersed by cyclic voltammetry (CV) on the working electrode. It is found that it can have a good catalytic ability, and has an electrochemical active surface area(EAS) of 291 m2∙g−1. In this research, we also used FMP to prepare nitrogen-doped graphene with nitrogen plasma and found that it has better catalytic ability for hydrogen evolution reaction(HER). Finally, the electrochemically activated sample was further measured for its hydrogen storage effect by PCT, and in the measurement results, it was found that the Pt/GP Ar25 at 2.33 wt% was better than the commercial 10 wt% Pt/C. It is attributed to the dispersion of nano-Pt particles on the samples after electrochemical activation and the excellent physical adsorption properties of graphene.

誌謝................................................................................................................................ i
摘要................................................................................................................................ ii
Abstract .......................................................................................................................... iii
第 1 章 緒論................................................................................................................... 1
1.1 研究動機........................................................................................................ 1
1.2 研究目的........................................................................................................ 3
第 2 章 文獻回顧與原理 ................................................................................................ 5
2.1 石墨烯製備.................................................................................................... 5
2.2 電漿增強化學氣相沉積法原理....................................................................... 7
2.2.1 化學氣相沉積法 (chemical vapor deposition, CVD) .................... 7
2.2.2 電漿增強化學氣相沉積法 (Plasma-enhanced chemical vapor
deposition, PECVD) ..................................................................... 7
2.3 石墨烯在電化學活化之應用 .......................................................................... 9
2.4 電化學分析原理............................................................................................. 11
2.4.1 氧化還原反應 (oxygen reduction reaction, ORR)......................... 11
2.4.2 法拉第定律 (Faraday’s law) ....................................................... 12
2.4.3 電雙層之機制 ................................................................................ 13
2.5 PCT 分析原理 ............................................................................................... 14
2.5.1 固態儲氫之機制............................................................................. 14
2.5.2 氫溢出效應 (spillover effect) ........................................................ 15
2.5.3 理想氣體方程式............................................................................. 16
第 3 章 實驗方法與儀器 ................................................................................................ 18
3.1 石墨烯製備.................................................................................................... 18
3.1.1 MPT 製備石墨烯........................................................................... 18
3.1.2 FMP 製備氮摻雜石墨烯................................................................ 19
3.2 材料分析........................................................................................................ 21
3.2.1 拉曼光譜分析 (Raman spectroscopy analysis).............................. 21
3.2.2 X 光光電子能譜儀 (X-ray Photoelectron Spectroscopy, XPS)..... 22
3.3 HER 實驗配置............................................................................................... 23
3.3.1 電極製備........................................................................................ 23
3.3.2 電化學量測裝置............................................................................. 24
3.4 電化學量測與分析......................................................................................... 24
3.5 PCT 量測與分析............................................................................................ 25
第 4 章 實驗量測結果與分析......................................................................................... 27
4.1 MPT 製備石墨烯粉末之材料分析 ................................................................. 27
4.1.1 沉積位置與石墨烯缺陷密度之關係 ............................................... 27
4.1.2 氣體流率與石墨烯缺陷密度之關係 ............................................... 29
4.2 FMP 製備氮摻雜石墨烯粉末之材料分析 ...................................................... 30
4.3 石墨烯作為分散載體於電化學儲氫之應用 .................................................... 36
4.3.1 GP 於不同缺陷下之電化學活化量測............................................. 37
4.3.2 GP 與不同碳材之電化學活化量測................................................. 39
4.3.3 GP 於不同金屬下之電化學活化量測............................................. 40
4.3.4 氮摻雜在電化學活化量測之影響................................................... 41
4.4 PCT 儲氫量測 ............................................................................................... 44
4.4.1 Pt 裝飾對氫氣儲存之效果 ............................................................. 44
4.4.2 GP 與不同碳材之 PCT 量測.......................................................... 46
4.4.3 氮摻雜對氫氣儲存之效果.............................................................. 49
第 5 章 總結與未來展望 ................................................................................................ 50
參考文獻......................................................................................................................... 52

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