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研究生: 宋承憲
Song, Cheng-Shian
論文名稱: 碳材上的磷化二元鎳鈷晶體對於產氫反應之催化效果探討
The effect of binary Nickel Cobalt Phosphide with Carbon black for Hydrogen Evolution Reaction
指導教授: 王禎翰
Wang, Jeng-Han
口試委員: 王禎翰
Wang, Jeng-Han
李積琛
Lee, Chi-Shen
吳樸偉
Wu, Pu-Wei
口試日期: 2022/06/23
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 120
中文關鍵詞: 析氫反應電化學化學氣相沉積法鎳鈷磷化物鎳鈷氧化物
英文關鍵詞: Hydrogen evolution, electrochemistry, chemical vapor deposition, Nickel Cobalt phosphide, Nickel Cobalt oxide
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202200760
論文種類: 學術論文
相關次數: 點閱:114下載:14
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  • 氫氣是一種未來能源的趨勢,可以取代目前在能源上大量使用的石油燃料,在本研究中,我們調整多種的鎳鈷比例 9/1, 5/1, 3/1, 2/1, 1/1, 1/2, 1/3, 1/5, 1/9。研究低成本的鎳鈷磷化物對產氫反應的活性。金屬氧化物利用溶膠凝膠共沉澱法並鍛燒後合成,然後通過化學氣相沉積法製備金屬磷化物。本研究利用能量散射光譜儀(EDX)、高解析耦合電漿光學發射光譜儀(ICP-OES)、X光光電子光譜(XPS)分析催化劑之表面及整體組成,利用X光粉末繞射儀(X-Ray Powder Diffraction analysis, XRD) 、掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 、穿透式電子顯微鏡(Transmission electron microscope, TEM)做晶體結構和表面結構分析。在產氫反應活性的測定,包括過電位和 Tafel 斜率,以及電化學活性表面積由電化學測量確定。本實驗的結果發現,Ni/Co = 1/1 的催化劑具有最好的 HER 活性,Tafel 斜率為 76.8 mV/dec,在-10 mA/cm2時過電位為 93 mV。根據鑑定結果,最好的催化劑Ni/Co=1/1有最大的ECSA為1641 cm2/g,並且樣品保持純Ni2P的晶型下參入Co,可以有效的提升過電位,傾向於 Volmer-Heyrovsky 反應機構並有良好的 Tafel 斜率。

    Hydrogen is a primosing energy and can replace the limited and polluted fossil fuels in the near futhre. In our present study, we examine hydrogen evolution reaction (HER) on low-cost nickel and cobalt phosphides with various Ni/Co ratios of 9/1, 5/1, 3/1, 2/1, 1/1, 1/2, 1/3, 1/5, 1/9. Metal oxides have been initially synthesized by sol-gel precipitation method. The phosphides were then fabricated by chemical vapor deposition method. The chemical and surface compositions were characterize by EDX, ICP-OES and XPS; crystallines and surface structures were analyzed by XRD, SEM, TEM; finally, the HER activity, including overpotential and Tafel slope, and ECSA were determinined by electrochemical measurements. Our results found that the catalyst with Ni/Co = 1/1 has the best HER activity with Tafel slope of 76.8 mV/dec and overpotential of 93 mV at 10 mA/cm2. According to the characterizations, the best catalyst of Ni/Co=1/1 shows the largest ECSA of 1641 cm2/g,and has the most purified Ni2P phase with Co doping, ,responsible for the lower overpotential, which favors for the Volmer-Heyrovsky mechanism and results the low Tafel slope.

    第一章 緒論 1 1-1前言 1 1-2產氫反應機制 2 1-3研究動機和實驗方法 6 第二章 實驗方法 9 2-1催化劑合成目的及原理 9 2-1-1催化劑合成目的 10 2-1-2 催化劑合成原理 11 2-2催化劑合成步驟 13 2-2-1氧化鎳鈷合成步驟 13 2-2-2 磷化鎳鈷合成步驟 16 2-3 實驗儀器原理及催化材料鑑定 20 2-3-1掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 、能量散射光譜儀(Energy Disperse X-Ray Spectroscopy, EDX) 21 2-3-2 X光粉末繞射儀(X-Ray Powder Diffraction analysis, XRD) 22 2-3-3穿透式電子顯微鏡(Transmission electron microscope, TEM) 24 2-3-4 X光光能子光譜儀(X-ray Photoelectron Spectroscopy, XPS) 24 2-3-5高解析耦合電漿光學發射光譜儀(Inductively Coupled Plasma Optical Emission Spectrometer, ICP-OES) 26 2-3-6鍛燒爐(Furnace) 26 2-3-7高溫管式爐(Oven) 27 2-4 電化學測量準備 27 2-4-1 電極系統及環境 28 2-4-2 電化學醬料製備 29 2-4-3 線性掃描伏安法(LSV) 30 2-4-4 電化學活性表面積(ECSA) 31 第三章 結果與討論 32 3-1不同組成鎳鈷磷化物(NixCoyP)析氫反應活性比較 32 3-1-1 XRD 32 3-1-2 SEM 51 3-1-3 EDX 54 3-1-4 TEM 57 3-1-5 XPS 60 3-1-6 ICP-OES 77 3-2 電化學測試 80 3-2-1 ECSA 80 3-2-2 LSV和Tafel slope 85 第四章 結論 93 參考資料 95 附錄 NiCoP定組成下製程對於析氫反應效果之影響 100 附錄 氧化鎳鈷製程 100 1-1 XRD 101 1-2 SEM 105 1-3 EDX 106 1-4 ECSA 107 1-5 LSV/Tafel slope 109 1-6不同氧化溫度下電化學結果綜合比較 110 附錄 單一組成下磷化製程對於NiCoP析氫反應電化學效果之影響 111 2-1 XRD 112 2-2 SEM 114 2-3 EDX 115 2-4 LSV和Tafel slope 117 2-5 ECSA 118 2-6不同磷化溫度下電化學結果綜合比較 119

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