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研究生： 方俐雯
Fang, Li-Wen
論文名稱： 合成鉬添加碳化鎢/還原氧化石墨烯做為電催化產氫觸媒之應用
Synthesis and Characterization of Mo-addition WC/rGO as Electrocatalyst for Hydrogen Evolution Reaction
指導教授： 黃肇瑞
Huang, Jow-Lay
共同指導: 王聖璋
Wang, Sheng-Chang
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 79
中文關鍵詞： 氫能 、過渡金屬碳化物 、碳化鎢 、水解製氫 、電觸媒 、水熱法 、濕式化學法 、鉬
外文關鍵詞： Hydrogen evolution reaction, Electrocatalysis, Transition metal carbide, Electrocatalyst, Tungsten carbide
相關次數： 點閱：196  下載：0 
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    • 化石燃料為現今社會仰賴的主要能源基礎．然而由於其資源有限，再加上燃燒化石燃料所造成的碳排放加劇暖化效應並引發氣候變遷，勢必需要發展其餘綠色替代能源。
    氫能源（Hydrogen Energy）為如今最具潛力的再生能源，具乾淨、效率、環保之特質。水分解產氫(Hydrogen evolution reaction by water splitting)用以生產氫能源，受限於反應效率低，需透過觸媒材料的使用，降低活化能障，催化反應的進行。鉑（Platinum, 白金）為現階段研究中展現最優秀電催性質之材料，然而其具稀少性，價格高昂，因此學界持續發展及尋找用以替代鉑的電觸媒材料。碳化鎢經理論計算及相關研究顯示，因材料具有與白金相似的電子結構，得以展現類白金催化性質，並應用於電催化反應。碳化鎢作為電極，具備良好導電性、優秀電催化能力、高穩定性、高耐腐蝕性、地球藏量足夠等優勢，在水分解產氫領域展現優秀的發展潛力。
    本研究藉由兩種液相方法結合煆燒的雙步驟反應進行碳化鎢觸媒材料的合成。其一為水熱合成法(Hydrothermal Method)，藉由去離子水作為溶劑分散鎢源及碳源於其中，進行攝氏220度、12小時的反應，使鎢源於高溫下析出於碳材料，並經第二步驟之煆燒，於攝氏900度煆燒兩小時，令碳擴散入鎢晶格形成δ-WC催化劑。其二由濕式化學法(Wet-chemistry Method)改善顆粒平均大小及含碳問題，令油胺作為溶劑，使鎢源、碳源、碳基材氧化石墨烯分散其中，結合形成前軀體，並經第二步驟煆燒，在900度-兩小時的環境中完成氧化石墨烯之還原及前軀體之碳化，合成WxC/rGO（x = 1, 2）催化劑，並藉由鉬源之添加，改變電子結構及增加W2C、Mo2C，進一步合成鉬修飾WxC-MoxC/rGO催化劑，其η10為196 mV，Tafel slope為76 mV/dec。
    本研究證明利用濕式化學法合成鉬添加碳化鎢/還原氧化石墨烯電催化劑運用於水分解產氫的效果，未來可望藉由實驗流程設計、摻雜不同金屬、導電基材更替等方式，研究活性位置之表現，更精準的提升表面性質及設計碳化鎢觸媒結構。

    Hydrogen has been considered as a promising alternative energy which is capable of taking place of fossil fuel. In this study, a transition metal carbide was synthesized to replace platinum, serving as electrocatalyst. We used two liquid phase reaction combined with high temperature sintering process to synthesize WC, WxC/rGO, WxC-MoxC/rGO, which include hydrothermal method and wet-chemistry method. DI water and oleylamine (OLA) were used as solvent respectively for the two method to disperse the tungsten reactant into carbon source. The second step is high-temperature carbonization heat treatment. During the 900°C-2hour heat-treatment, the environment provide energy for precursor to crystallize to form tungsten carbide. As the same time, graphene oxide is reduced to reduced graphene oxide (RGO) at such a high temperature. The WxC-MoxC/rGO catalyst performs a -170mV over potential at 10mA and 76mV dec-1 Tafel slope while some further analysis were conducted with TEM, SEM, Raman, XRD, and XPS.

    中文摘要 I Extended Abstract III 誌謝 XII 論文總目錄 XIV 表目錄 XVII 圖目錄 XVIII 第一章 緒論 1 1.1 前言 1 1.2 碳化鎢應用背景 3 1.3 研究動機與目的 3 第二章、文獻回顧 5 2.1 水分解產氫（Water Splitting for Hydrogen Evolution Reaction, HER） 5 2.2 電催化劑 13 2.2.1 電催化劑電催化劑選用條件 13 2.2.2. 電催化劑性質評斷參數 15 2.2.3. 電催化材料 20 2.3 碳化鎢 (Tungsten Carbide) 25 2.3.1 結構與相組成 25 2.3.2 催化表現能力 27 2.3.3 製程 28 第三章、實驗方法 29 3.1 實驗藥品 29 3.2 實驗裝置 30 3.2.1 水熱反應裝置 30 3.2.2 迴流（reflux）系統 31 3.2.3 管型高溫爐 32 3.2.4 電化學量測裝置 33 3.3 實驗製程 34 3.3.1 碳化鎢催化劑合成（水熱法） 34 3.3.2 碳化鎢催化劑合成（WxC/rGO, x=1,2） 35 3.3.3 鉬添加碳化鎢催化劑合成（WxC-MoxC/rGO, x=1,2） 36 3.3.4 氧化石墨烯（graphite oxide）合成 37 3.3.5 產氫工作電極製備(Preparation of working electrode) 38 3.4 材料鑑定分析 39 3.4.1 X-ray繞射分析儀 (X-ray diffraction spectrometer: XRD) 39 3.4.2 高解析場發射掃描式電子顯微鏡 (High Resolution Field Emission Scanning Electron Microscopy:FE-SEM) 41 3.4.3 高解析穿透式電子顯微鏡 (Ultrahigh Resolution Analytical Electron Microscopy:HR-AEM) 42 3.4.4 拉曼光譜分析儀 (Raman Spectrometer, ) 43 3.4.5 電子能譜化學分析儀 (Electron Spectroscopy for Chemical Analysis:ESCA) 44 3.4.6電化學性質分析量測 45 第四章、結果與討論 46 4.1 水熱合成碳化鎢球狀電觸媒 46 4.1.1 晶相分析 46 4.1.2 微結構分析 48 4.1.3 拉曼分析 51 4.1.4 電催化產氫效能與討論 52 4.2 液相化學環境合成碳化鎢-還原氧化石墨烯(WxC/rGO) 54 4.2.1 晶相分析 54 4.2.2 微結構分析 55 4.2.3 拉曼分析 58 4.2.4 價數態與元素能譜分析 60 4.2.5 電催化產氫效能與討論 61 4.3 液相化學環境合成碳化鎢/鉬-還原氧化石墨烯 63 4.3.1 晶相分析 63 4.3.2 微結構分析 65 4.3.3 電催化產氫效能與討論 68 第五章、結論與未來展望 73 參考文獻 74

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