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研究生： 林奕亨
Lin, Yi-Heng
論文名稱： 以液相化學法合成過渡金屬鈷碳化物應用於電解催化製氫之研究
Highly active electrocatalyst cobalt-carbide nanoparticles synthesized by wet-chemistry method for hydrogen evolution reaction
指導教授： 黃肇瑞
Huang, Jow-Lay
共同指導教授: 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： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 92
中文關鍵詞： 氫能 、過渡金屬碳化物 、碳化鈷 、濕式化學法 、水解製氫 、電觸媒
外文關鍵詞： Hydrogen energy, transition metal carbides, cobalt carbides, hydrogen evolution reaction, electrocatalyst
相關次數： 點閱：187  下載：4 
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    • 氫能是具有前景的替代能源之一，水分解產氫(Hydrogen evolution reaction by water splitting)為其一關鍵製程，尋找高效能之非貴重金屬催化劑成為氫能是否能普及的關鍵。碳化鈷奈米粒子(Cobalt carbide nanoparticles, CoxC NPs, x=2,3)是一項相當新穎的材料，由理論計算值與近年研究顯示，其具有與Pt相似的電子結構，作為HER反應之電極其具有良好的電學性質、高導電性、耐酸性環境、高穩定性及高耐久性等優點。本研究成功利用相對低溫且無須加壓之濕式液相化學合成技術，藉由乙酸鈷（Cobalt(II) acetate）、三甘醇（Triethylene glycol）與氫氧化鈉，合成出CoxC (x=2, 3)複合相碳化鈷奈米晶體，但反應完成度較低，部分前驅物殘留，且結晶度不佳；當改以乙酸鈷、三甘醇及油胺（Oleylamine）做為原料時，其產物為結晶度較佳且均勻分散的純相Co2C奈米晶體，尺寸約為80 nm，兩者皆表現出高電催化活性。進一步將CoxC 與Co2C進行比較，藉由三電極系統進行電化學量測，CoxC製備之電極起始電位為 - 0.33V，塔弗斜率為91 mV/dec；而Co2C之起始電位為 - 0.27V，塔弗斜率為60mV/dec。於同樣的施加電壓下，Co2C電極表現出更高的電流密度，藉由電化學阻抗譜分析擬合出的等效電路，可得到電荷轉移電阻Rct (CoxC)=10.05 kΩ、Rct (Co2C)=6.02 kΩ，證明了Co2C能夠更有效的傳輸電荷。以上實驗結果證明了碳化鈷奈米粒子應用於催化水分解產氫反應上的潛力，未來可望藉由優化產物尺寸、載體結構或是摻雜等方式進一步改善材料表面性質，發展更低成本、高活性及穩定性之人造電催化產氫電極。

    Hydrogen is a promising alternative energy without greenhouse gas emissions. Since the transition metal carbides (TMCs) exhibited similarly electronic properties with noble metal platinum, they are considered sustainable alternatives to noble metals in catalysis. Among the TMCs, CoxC (x=2,3) nanoparticles (NPs) can act as an excellent electrocatalyst for hydrogen evolution reaction (HER) by water splitting. In our report, CoxC nanocomposites were synthesized by wet chemistry method using Cobalt (II) acetate, sodium hydroxide as precursors and triethylene glycol (TEG) as solvent. In addition, Co2C NPs were synthesized by similar wet chemistry method using Cobalt (II) acetate as precursors and TEG, oleylamine (OAm) as solvent. The cobalt carbide NPs exhibited high electrocatalytic activity. CoxC nanocomposites performed a -0.33V onset potential and 91mV/dec tafel slope, while the Co2C NPs exhibited a better performance of -0.27V and 60mV/dec respectively.

    中文摘要 I Extended Abstract II 致謝 XIII 總目錄 XV 圖目錄 XVIII 表目錄 XXI 第一章 緒論 1 1-1. 前言 1 1-2. 碳化鈷的發展 4 1-3. 碳化鈷奈米粒子應用於水分解產氫之發展 6 1-4. 研究動機與目的 6 第二章 文獻回顧 9 2-1. 水分解產氫反應 (Water Splitting for Hydrogen Evolution Reaction) 9 2-2. 電催化劑（Electrocatalyst） 16 2-2-1. 電催化劑選用要求 16 2-2-2. 評斷電催化劑性質之參數 18 2-2-3. 常用的電催化材料 23 2-3. 碳化鈷 (Cobalt carbide, Co2C and Co3C) 29 2-3-1. 結構與相構成 30 2-3-2. 催化性值 31 2-3-3. 製程 33 第三章 研究方法與實驗步驟 37 3-1. 實驗藥品 37 3-2. 實驗設備 38 3-2-1. 迴流（reflux）裝置 38 3-2-2. 電化學量測設備 39 3-3. 實驗流程 40 3-3-1. CoxC奈米粒子合成 (x=2, 3) 40 3-3-2. Co2C奈米粒子合成 42 3-3-3. 製備工作電極 (Working electrode preparation) 44 3-4. 材料鑑定及分析 45 3-4-1. X-ray繞射分析儀 (X-ray diffraction spectrometer, XRD) 45 3-4-2. 電子能譜化學分析儀 (Electron Spectroscopy for Chemical Analysis, ESCA) 46 3-4-3. 掃描式電子顯微鏡 (scanning electron microscopy, FE-SEM) 47 3-4-4. 高解析分析電子顯微鏡 (Ultrahigh Resolution Analytical Electron Microscopy, HR-AEM) 48 3-4-5. 電化學性質分析 49 第四章 結果與討論 50 Part 1 製程與微結構分析 50 4-1. CoxC奈米粒子 (x=2,3) 50 4-1-1. 晶相分析 52 4-1-2. 價數態與元素能譜分析 54 4-1-3. 微結構分析 56 4-1-4. 小結 60 4-2. Co2C奈米粒子 61 4-2-1. 晶相分析 63 4-2-2. 價數態與元素能譜分析 65 4-2-3. 微結構分析 67 4-2-4. 小結 71 Part 2 電催化效能 72 4-3. 電催化產氫效能量測與機制探討 72 4-3-1. LSV起始電位分析 73 4-3-2. 塔弗斜率Tafel slope 75 4-3-3. 電化學阻抗譜分析(Electrochemical impedance spectroscopy) 77 4-3-4. 小結 79 第五章 結論 81 第六章 參考文獻 83

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