博碩士論文 111329014 詳細資訊




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姓名 孫秉蔚(Ping-Wei Sun)  查詢紙本館藏   畢業系所 材料科學與工程研究所
論文名稱 銅-鋅微柱之製備及其在二氧化碳還原電催化之選擇性
(Fabrication of Copper-Zinc Micropillars and Selectivity in Electrocatalytic Carbon Dioxide Reduction)
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檔案 [Endnote RIS 格式]    [Bibtex 格式]    [相關文章]   [文章引用]   [完整記錄]   [館藏目錄]   至系統瀏覽論文 (2026-7-31以後開放)
摘要(中) 近年來,二氧化碳濃度上升,導致全球暖化加劇。因此,透過二氧化碳還原反應(CO2 Electrochemical Reduction Reaction, CO2RR),將二氧化碳轉化為高附加價值之化學品,可以實現碳中和之目標。本研究以微陽極導引電鍍法(Micro-Anode Guided Electroplating, MAGE)製備銅鋅合金微柱,並探討其在0.1 M KHCO3中進行CO2RR之產物。固定析鍍偏壓為4.6 V、間距控制在40 μm,改變硫酸鋅濃度(0.15 ~ 0.18 M)進行析鍍。合金微柱(Cu74Zn26、Cu66Zn34、Cu63Zn37、Cu55Zn45)經SEM、EDX、XRD分析材料特性。此製程所得微柱具有三維結構,增加催化活性面積。隨後,利用循環伏安法、線性掃描伏安法、電化學交流阻抗頻譜、計時電流法於0.1 M KHCO3下分析其電催化性能,結果顯示:CZ16合金微柱(組成為Cu66Zn34)具有最大之電化學活性表面積(Electrochemical Surface Area, ECSA)為8.7 cm2。此外,在-1.0 V vs. RHE下,具有最小之(乙醇)塔弗斜率(Tafel slope)為185 mV/dec。最後,藉由GC、NMR、FTIR分析CO2RR後之產物。結果顯示:CZ16合金微柱(組成為Cu66Zn34)還原為乙醇,在-1.0 V vs. RHE下,具有最高之法拉第效率(Faradaic Efficiency, FE)為35.0 %,乙醇之選擇性(Selectivity)為51.2 %。此外,CO2RR後成分變化增加催化面積,顯示其為銅鋅雙金屬異質電極。
摘要(英) In recent years, the rising concentration of carbon dioxide has exacerbated global warming. Therefore, converting carbon dioxide into high-value chemicals through the CO2 Electrochemical Reduction Reaction (CO2RR) can achieve the goal of carbon neutrality. This study employs Micro-Anode Guided Electroplating (MAGE) to prepare Cu-Zn alloy micro-columns and investigates the products obtained from CO2RR in 0.1 M KHCO3. The alloy micro-columns (Cu74Zn26, Cu66Zn34, Cu63Zn37, Cu55Zn45) were synthesized by setting a fixed plating bias of 4.6 V and spacing control at 40 μm while varying zinc sulfate concentration (0.15~0.18 M). The material characteristics were analyzed using SEM, EDX, and XRD. The resulting micro-columns feature a three-dimensional structure, increasing the catalytic active surface area. Subsequently, electrochemical performance was analyzed using cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy, and chronoamperometry in 0.1 M KHCO3. Results indicate that CZ16 alloy micro-column (composition Cu66Zn34) has the largest Electrochemical Surface Area (ECSA) of 8.7 cm². Additionally, at -1.0 V vs. RHE, it shows the lowest Tafel slope (for ethanol) of 185 mV/dec. Finally, GC, NMR, and FTIR were used to analyze the products post-CO2RR. Results show that CZ16 alloy micro-column (composition Cu66Zn34) reduces to ethanol, with the highest Faradaic Efficiency (FE) of 35.0 % and selectivity for ethanol at 51.2 % at -1.0 V vs. RHE. Furthermore, compositional changes after CO2RR increase the catalytic surface area, confirming it as a Cu-Zn bimetallic heterogeneous electrode.
關鍵字(中) ★ 銅鋅合金
★ 微陽極導引電鍍法
★ 二氧化碳還原反應
★ 乙醇
★ 選擇性
★ 法拉第效率
關鍵字(英) ★ Cu-Zn alloy
★ Micro-Anode Guided Electroplating
★ CO2 Reduction Reaction
★ Ethanol
★ Selectivity
★ Faradaic Efficiency
論文目次 摘要 i
Abstract ii
致謝 iv
目錄 v
表目錄 ix
圖目錄 xiv
第一章 緒論 1
1-1 研究背景 1
1-2 研究動機與目的 2
第二章 文獻回顧 5
2-1 合金電鍍原理 5
2-2 微陽極導引電鍍法之發展 6
2-2-1 Cu-Zn合金微柱 6
2-2-2 析氫反應(Hydrogen Evolution Reaction, HER) 7
2-2-3 析氧反應(Oxygen Evolution Reaction, OER) 7
2-3 二氧化碳還原反應(Carbon Dioxide Reduction Reaction, CO2RR) 8
2-3-1 反應機制 8
2-3-2 產物 9
2-4 電催化劑 13
2-4-1 Cu-Au 13
2-4-2 Cu-Zn 14
2-4-3 Cu-Ag 16
2-4-4 Cu-Sn 17
第三章 研究方法 18
3-1 實驗架構 18
3-2 微陽極導引電鍍裝置 21
3-3 微陽極與陰極製備 21
3-4 藥品配方 22
3-5 材料特性分析 23
3-5-1 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 23
3-5-2 能量散射光譜儀(Energy-Dispersive X-ray spectroscopy, EDS) 23
3-5-3 X光繞射儀(X-ray Diffractometer, XRD) 24
3-5-4 聚焦離子束(Focus Ion Beam, FIB) 25
3-5-5 穿透式電子顯微鏡(Transmission Electron Microscopy, TEM) 26
3-5-6 X光光電子能譜儀(X-ray Photoelectron Spectroscopy, XPS) 27
3-6 電化學分析 28
3-6-1 電化學系統 28
3-6-2 電化學活性表面積(Electrochemical Surface Area, ECSA) 29
3-6-3 線性掃描伏安法(Linear Sweep Voltammetry, LSV) 30
3-6-4 電化學阻抗頻譜(Electrochemical Impedance Spectroscopy, EIS) 30
3-6-5 計時電流法(Chronoamperometry, CA) 31
3-7 產物分析 31
3-7-1 氣相層析儀(Gas Chromatography, GC) 31
3-7-2 核磁共振儀(Nuclear Magnetic Resonance, NMR) 32
3-7-3 傅立葉轉換紅外光譜儀(Fourier-Transform Infrared Spectroscopy FTIR) 35
第四章 結果與討論 36
4-1 二氧化碳還原反應前後特性之探討 36
4-1-1 表面形貌分析 SEM 36
4-1-2 成分元素分析 EDX 42
4-1-3 晶體結構分析 XRD 46
4-1-4 顯微結構分析 TEM 65
4-1-5 表面元素分析 XPS 68
4-2 電催化性能之探討 72
4-2-1 電化學活性表面積 ECSA 72
4-2-2 線性掃描伏安法 LSV 78
4-2-3 電化學阻抗頻譜 EIS 82
4-2-4 計時電流法 CA 88
4-3 二氧化碳還原產物之探討 93
4-3-1 氣相產物定量分析 GC 93
4-3-2 液相產物定量分析 NMR 97
4-3-3 官能基結構鑑定 FTIR 106
4-3-4 二氧化碳還原反應之催化性能分析 107
第五章 結論與未來展望 109
參考文獻 110
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指導教授 林景崎(Jing-Chie Lin) 審核日期 2024-7-30
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