本研究為製備直接甲醇燃料電池 (Direct Methanol Fuel Cell, DMFC) 之鉑-三氧化鎢/碳 (Pt-WO3/C) 陽極催化劑與其性質之研究，目的為開發對甲醇氧化反應 (Methanol oxidation reaction, MOR) 效能有提升之電催化劑。
一般 DMFC 使用以 Pt 為主成份之電催化劑進行 MOR，往往因為 CO 毒化現象的發生，造成 Pt 表面吸附一層不易移除之 CO 分子，使得 DMFC 的發電效能快速衰減。本研究嘗詴於傳統 Pt/C 電催化劑中加入三氧化鎢 (WO3) 奈米顆粒，以期能提高電催化劑抵抗 CO 毒化的能力，進而提升 MOR 效能。本研究以六氯化鎢 (tungsten hexachloride, WCl6) 為起始物，使用二甲基甲醯胺 (N,N-dimethyl-formamide, DMF) 為溶劑，以經過 NaOH 前處理或未經前處理之 Vulcan XC-72 為碳載體，先將 WO3 製備於碳載體上成為 WO3/C 奈米複合材料，然後利用多元醇還原法 (Polyol method)，以乙二醇同時做為還原劑與溶劑，將 Pt 奈米顆粒製備於 WO3/C 上，取得 Pt-WO3/C 電催化劑。本研究使用 X 光繞射分析儀 (X-ray diffractometer, XRD)、穿透式電子顯微鏡 (transmission electron microscope, TEM)、掃描式電子顯微鏡 (scanning electron microscope, SEM)、傅立葉轉換紅外線吸收光譜儀 (fourier transform infrared spectroscopy, FT-IR) 與元素分析 (energy dispersive X-ray spectrometer, EDS) 等儀器，測量製備所得電催化劑之表面形態與成份，並使用循環伏安法 (cyclic voltammetry,CV)，計時安培法 (chronoamperometry, CA) 進行 MOR 效能、電化學活性表面積 (electrochemical active surface area, EASA)、CO 脫附與反應穩定性等電化學特性分析。 使用不同濃度 WCl6/DMF 溶液為起始物，以未經前處理之碳載體製備 WO3/C，經 450℃ 燒結所得之 PtW(0.06 ~ 0.14)/C450 系列電催化劑，WO3 奈米顆粒形成約 50 ~ 150 nm 之聚集，且其 MOR 效能低於市售 E-TEK Pt/C 電催化劑。使用經 NaOH 前處理過之碳載體，於相同條件下製得之 PtW(0.06 ~ 0.14)/Cs450 系列電催化劑，雖然 WO3 奈米顆粒仍呈現聚集狀態，但其 MOR 效能可獲得明顯提升。使用經前處理之碳載體，並改變 WO3/C 之燒結溫度為 200℃ 製備所得之 PtW(0.06 ~ 0.14)/Cs200 系列電催化劑，可得非晶形狀態(amorphous) 之 WO3 奈米顆粒均勻分佈於碳載體上，且其 MOR 效能皆高於市售 E-TEK Pt/C 電催化劑。其中 PtW(0.08)/Cs200 電催化劑於本研究中展現最佳之 MOR 效能，於相同 CV 實驗條件下，其 MOR 峰電流值為 873 ± 96 A/g-Pt，約 2.2 倍高於市售 E-TEK Pt/C 電催化劑 (389 ± 56 A/g-Pt)。於計時安培法之測量下也顯示 PtW(0.08)/Cs200 電催化劑具有最佳抵抗 CO 毒化的能力，於 1000 秒後之穩定電流密度值 (28.0 A/g-Pt) 約 11 倍高於市售 E-TEK Pt/C 電催化劑。

The major goals of this research are the preparation and characterization of Pt-WO3/C electrocatalysts for the methanol oxidation reaction (MOR) at the anode of a direct methanol fuel cell (DMFC). Pt-based electrocatalysts were generally employed as the anode electrocatalysts for DMFCs. However, the surface of Pt could be easily occupied by intermediates generated during MOR (especially CO), which are difficult to be removed and leading to a rapid decrease in the DMFC performance. Such phenomenon is known as “CO-poisoning” phenomenon. In this study, WO3 nanoparticles were synthesized and added to conventional Pt/C to give Pt-WO3/C electrocatalysts in order to enhance the MOR efficiencies as well as the CO-tolerance abilities.
The Pt-WO3/C electrocatalysts were prepared by two-step procedure. N,N-Dimethyl-formamide (DMF) solution of tungsten hexachloride (WCl6) was used as the precursor, and the WO3/C nanocomposites were firstly synthesized. Then, Pt nanoparticles were decorated onto the WO3/C nanocomposites by polyol method using ethylene glycol (EG) as both the reducing agent and solvent to obtain the Pt-WO3/C electrocatalysts. X-ray diffractometer (XRD)、transmission electron microscope (TEM)、scanning electron microscope (SEM)、fourier transform infrared spectroscopy (FT-IR) and energy dispersive X-ray spectrometer (EDS) were used to investigate the surface morphologies and compositions of the electrocatalysts. The MOR efficiency, electrochemical active surface area (EASA), CO stripping and MOR stability of the electrocatalysts were evaluated by cyclic voltammetry (CV) and chronoamperometry (CA) experiments.
For the PtW(0.06 ~ 0.14)/C450 series electrocatalysts using pristine Vulcan XC-72 carbon black as the support and calcined at 450 oC, the WO3 nanoparticle aggregates with sizes of 50 ~ 200 nm were obtained, and their MOR efficiencies were all lower then the commercial E-TEK Pt/C electrocatalyst. The MOR efficiencies were sighificantly improved for the PtW(0.06 ~ 0.14)/Cs450 series electrocatalysts using NaOH-pretreated Vulcan XC-72 carbon black as the support, however the aggregates of WO3 nanoparticles were still observed. In order to avoid the aggregation of WO3 nanoparticles, the PtW(0.06 ~ 0.14)/Cs200 series electrocatalyst were synthesized using NaOH-pretreated Vulcan XC-72 carbon black and calcined at 200 oC. Evenly distributed amorphous WO3 nanoparticles on carbon support were obtained and confirmed by XRD and TEM investigates. The MOR efficiencies as well as the CO-tolerance abilities of these electrocatalysts were all higher than the commercial E-TEK Pt/C electrocatalyst. The PtW(0.08)/Cs200 electrocatalyst achieved the highest MOR efficiency of 873 ± 96 A/g-Pt among all the electrocatalysts prepared in this study, and which was about 2.2 times higher than that of the commercial E-TEK Pt/C electrocatalyst (389 ± 56 A/g-Pt).

中文摘要 ......................................................................................................... I
英文摘要 .......................................................................................................III
圖目錄 .......................................................................................................... IX
表目錄 ................................................................................................................. XIV
第一章 緒論............................................................................................................. 1
1.1 前言 ............................................................................................................ 1
1.2 直接甲醇燃料電池簡介 ............................................................................. 4
1.2.1 工作原理 ......................................................................................... 4
1.2.2 電催化甲醇氧化反應機制 .............................................................. 7
1.2.3 發展面臨之問題 .............................................................................. 8
1.3 甲醇氧化之電催化劑 ................................................................................. 9
1.3.1 雙元合金電催化劑 (Binary metal alloy electrocatalysts) ................ 9
1.3.2 鉑-金屬氧化物電催化劑 ................................................................ 11
1.3.3 碳載體的應用 ................................................................................ 13
1.4 研究動機與目的 ..................................................................................... 16
第二章 文獻回顧 ................................................................................................... 17
2.1 以碳為載體之 Pt-WO3/C 電催化劑 ....................................................... 17
2.2 以 WO3 為載體之 Pt/WO3 電催化劑 ................................................... 22
2.3 以導電材料為基材之 Pt-WO3 電催化劑 ............................................... 24
2.4 碳載體表面修飾之文獻回顧 ................................................................... 26
第三章 實驗........................................................................................................... 27
3.1 實驗藥品及材料 ...................................................................................... 27
3.2 實驗設備 .................................................................................................. 28
3.3 Pt/C電催化劑製備方法步驟 .................................................................... 29
3.4 WO3 奈米顆粒製備方法之選擇 .............................................................. 31
3.4.1 WO3 奈米顆粒製備方法之步驟 .................................................... 32
3.5 碳載體之前處理 ...................................................................................... 36
3.6 以 WCl6 前驅物製備 Pt-WO3/C 電催化劑 ........................................... 36
3.6.1 實驗架構 ....................................................................................... 37
3.6.2 WO3/C 奈米複合材料之製備 ........................................................ 38
3.7 表面型態與性質分析 ............................................................................... 40
3.7.1 X 光繞射分析儀 ............................................................................ 40
3.7.2 穿透式電子顯微鏡 ........................................................................ 40
3.7.3 掃描式電子顯微鏡 ........................................................................ 40
3.7.4 傅立葉轉換紅外線吸收光譜儀 ..................................................... 40
3.8 電化學分析方法 ...................................................................................... 41
3.8.1 循環伏安法 ................................................................................... 41
3.8.2 計時安培法 ................................................................................... 46
3.8.3 電化學活性表面積 ........................................................................ 47
第四章 Pt-WO3/C 電催化劑製備方法之選擇 ...................................................... 49
4.1 Pt 奈米顆粒製備方法之選擇 ................................................................... 49
4.2 WO3 奈米顆粒製備方法之選擇 .............................................................. 58
4.2.1 以鎢粉製備 WO3奈米顆粒 .......................................................... 59
4.2.2 以鎢酸鈉 (Na2WO4‧2H2O) 製備 WO3奈米顆粒...................... 70
4.2.3 以磷鎢酸 (H3PW12O40) 製備 WO3奈米顆粒 .............................. 75
4.2.3 以氯鎢酸 (WCl6) 製備 WO3 奈米顆粒 ...................................... 78
4.3 以 NaOH 對碳載體進行前處理 ............................................................. 82
4.3.1 碳載體 XC-72 之前處理 ............................................................. 82
4.3.2 結構與結晶分析 ............................................................................ 83
4.3.3 表面形態與元素分析 .................................................................... 87
4.3.4 電化學分析結果 ............................................................................ 89
第五章 Pt-WO3/C 電催化劑 MOR 效能最佳化 ................................................. 92
5.1 碳載體之前處理與 WCl6 濃度之影響 ................................................... 92
5.1.1 XRD 晶型結構分析....................................................................... 93
5.1.2 TEM 表面形態與結構分析 ........................................................... 94
5.1.3 電催化甲醇氧化反應之效能........................................................104
5.2 燒結溫度之影響 .....................................................................................108
5.2.1 XRD 晶型結構分析與 TEM 表面型態與元素分析 ...................109
5.2.2 電催化甲醇氧化反應之效能........................................................ 115
5.3 電催化劑效能比較.................................................................................. 118
5.3.1 電催化甲醇氧化反應之效能........................................................120
5.3.2 CO 脫附實驗 ................................................................................122
5.3.3 計時安培法之穩定性效能測詴 ....................................................123
第六章 結論..........................................................................................................126
建議 .......................................................................................................................129

參考文獻 ...............................................................................................................130
附錄 A ..................................................................................................................143
附錄 B...................................................................................................................149

圖目錄
圖 1-1. DMFC工作原理。……………………………………………………………5
圖 1-2. DMFC 過電壓成因。【4】……………………………………………………6
圖 1-3. 雙功效應示意圖。…………………………………………………………10
圖 1-4. 理想之催化劑於載體上之分佈情形。……………………………………15
圖 1-5. Vulcan XC-72 碳載體之 TEM 圖。………………………………………15
圖 2-1. HRTEM images and associated nano-EDS measurements of Pt-WOx/C electrodes. EDS analysis was performed by reducing the size of the beam and focusing on the area as shown in the pictures.【71】……………………………17
圖 2-2. a TEM image for the sample of Pt–WO3/MWCNT, and b–e the corresponding EDS elemental mapping for the image in a. 【73】……………19
圖 2-3. TEM images of (a) Pt/C, (b) WO3/C, (c) Pt/WO3–C and (d) Pt/WO3–C–HT samples. 【66】…………………………………………………………………20
圖 2-4. TEM images of (A) WO3/C-1 and (B) WO3/C-2. 【67】……………………21
圖 2-5. (a) SEM image of WO3 microspheres, (b) HRTEM image of WO3 microspheres, (c) Lattice image of WO3 microspheres. 【75】…………………23
圖 3-1. Pt-WO3/C 電催化劑之製備流程圖。………………………………………31
圖 3-2. 實驗架構及流程。………………………………………………………37
圖 3-3. WO3 奈米複合材料製備流程。……………………………………………37
圖 3-4. 三極式電化學系統。………………………………………………………42
圖 3-5. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………43
圖 3-6. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 飽和 CO 水溶液之循環伏安圖。電位掃描速率為 50 mV/s。…………………………………………………45
圖 3-7. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液之計時安培法曲線圖。定電位為 0.5 V vs. Ag/AgCl。掃描時間為 1000 秒。…………46
圖 3-8. E-TEK Pt/C 電催化劑於 0.5 M 硫酸水溶液之循環伏安圖。電位掃描速率為 50 mV/s。………………………………………………………………48
圖 4-1. Pt/C 電催化劑製備流程。…………………………………………………49
圖 4-2. Pt/C-SBH電催化劑之 TEM 圖。…………………………………………51
圖 4-3. Pt/C-SBH TEM – EDAX 表面元素分析。………………………………51
圖 4-4. Pt/C-RME 電催化劑之 (a) TEM圖與 (b) HR-TEM 圖。………………53
圖 4-5. Pt/C-EGR 電催化劑之 (a) TEM 圖與 (b) HR-TEM 圖。……………55
圖 4-6. Pt/C-EGR 電催化劑之 TEM–EDS 表面元素分析。…………………55
圖 4-7. Pt/C-EGR與 E-TEK Pt/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。…………………………57
圖 4-8. Pt/C-EGR 與 E-TEK Pt/C 電催化劑於 0.5 M H2SO4 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………57
圖 4-9. WO3 奈米顆粒製備流程。………………………………………………58
圖 4-10. (a) PTA1/C、(b) PTA2/C、(c) PTA3/C 複合材料之 TEM 圖。……………61
圖 4-11. PtPTA1/C 與 PtPTA3/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………61
圖 4-12. (a) PTA1/ C、(b) PTA2/ C 與 (c) PTA3/ C 複合材料之 TEM–EDS 表面元素分析。………………………………………………………………………62
圖 4-13. (a) PtPTA1/C 與 (b) PtPTA3/C 電催化劑之 TEM 圖。………………63
圖 4-14. PtPTA4/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………64
圖 4-15. PtPTA4/C 電催化劑之 TEM 圖。………………………………………65
圖 4-16. PtPTA5/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………66
圖 4-17. PtPTA5/C 電催化劑之 TEM 圖。………………………………………67
圖 4-18. PtPTA6/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………68
圖 4-19. PtPTA6/C 電催化劑之 TEM 圖。………………………………………69
圖 4-20. PtNW1/C 電催化劑之 TEM 圖。………………………………………71
圖 4-21. PtNW1/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………72
圖 4-22. PtNW2/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………73
圖 4-23. PtNW2/C 電催化劑之 TEM 圖。………………………………………74
圖 4-24. PtPWA/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………76
圖 4-25. (a) PWA/C 複合材料與 (b) PtPWA/C 電催化劑之 TEM 圖。………77
圖 4-26. PtWC/C 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………79
圖 4-27. (a) WC/C 複合材料與 (b) PtWC/C 電催化劑之 TEM 圖。…………80
圖 4-28. 碳載體於 DMF 溶劑中分散情形。(左) 未經前處理之碳載體 (C)、(右) 經 NaOH 前處理之碳載體 (Cs)。…………………………………………82
圖 4-29. NaOH 處理過程中之表面反應示意圖。【98】……………………………83
圖 4-30. 未經 NaOH 前處理之碳載體 (C) 與經 NaOH 前處理之碳載體 (Cs) 之FTIR 圖譜。………………………………………………………………84
圖 4-31 XC-72 碳載體處理前後之 XRD 圖譜；(a)未經 NaOH 前處理之碳載體C，(b) 經 NaOH 前處理之碳載體 Cs。……………………………………86
圖 4-32. Pt/C 系列電催化劑之 XRD 圖譜。(a) Pt/Cs，(b) Pt/C 與 (c) E-TEK Pt/C。……………………………………………………………………..……86
圖 4-33. (a) 與 (b) 為 Pt/Cs 電催化劑之 TEM 圖與 (c) 之粒徑分佈分析圖。……………………………………………………………………………88
圖 4-34. Pt/Cs TEM – EDS 表面元素分析。……………………………….…........88
圖 4-35. E-TEK Pt/C、Pt/C-EGR 與 Pt/Cs 電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………91
圖 4-36. E-TEK Pt/C、Pt/C-EGR 與 Pt/Cs 電催化劑於 0.5 M H2SO4 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。…………………………………91
圖 5-1. PtW(0.06~0.14)/C450 系列電催化劑之 XRD 分析圖譜。….…………97
圖 5-2. PtW(0.06~0.14)/Cs450 系列電催化劑之 XRD 分析圖譜。……………98
圖 5-3. PtW(0.06 ~ 0.14 M)/C450 系列電催化劑之 TEM 分析圖。……………99
圖 5-4. PtW(0.06~0.14M)/Cs450 系列電催化劑之 TEM 分析圖。…………100
圖 5-5. W(0.14)/C450 電催化劑之 TEM–Mapping 掃描元素分析。(a) TEM 圖、(b) C 元素分佈、(c) O 元素分佈、(d) W 元素分佈。………………………101
圖 5-6. PtW(0.10)/C450 之 TEM 分析圖。(a) TEM 圖、(b) 選區繞射分析、(c) HR-TEM 圖。…………………………………………………………………103
圖 5-7. PtW/C450 系列電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。………………………………………106
圖 5-8. PtW/Cs450系列電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。………………………………………106
圖 5-9 . PtWC/450 與 PtW/Cs450 系列電催化劑之 MOR 效能趨勢圖。.....107
圖 5-10. PtW(0.06~0.14)/Cs200 系列催化劑之 XRD 分析圖譜。……………111
圖 5-11. PtW(0.06~0.14M)/Cs200 系列電催化劑之 TEM 分析圖。…………112
圖 5-12. PtW(0.08)/Cs200 電催化劑之 TEM–Mapping掃描元素分析。(a) TEM 圖、(b) Pt 元素分佈、(c) W 元素分佈。……………………………………114
圖 5-13. PtWCs200系列電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………117
圖 5-14. PtW/Cs200 系列電催化劑之 MOR 效能趨勢圖。……………………117
圖 5-15. 三系列催化劑之趨勢圖比較。…………………………………………119
圖 5-16. E-TEK Pt/C、PtW(0.10)/C450、PtW(0.12)/Cs450 與PtW(0.08)/Cs200電催化劑於 0.5 M H2SO4 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。…………………………………………………………………………121
圖 5-17. E-TEK Pt/C、PtW(0.10)/C450、PtW(0.12)/Cs450 與PtW(0.08)/Cs200電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………………………122
圖 5-18. E-TEK Pt/C、PtW(0.10)/C450、PtW(0.12)/Cs450 與PtW(0.08)/Cs200
電催化劑於飽和 CO 之 0.5 M H2SO4 水溶液中之循環伏安圖。電位掃描速率為 50 mV/s。……………………………………………………………124
圖 5-19. E-TEK Pt/C、PtW(0.10)/C450、PtW(0.12)/Cs450 與PtW(0.08)//Cs200
電催化劑於 0.5 M H2SO4 + 1.0 M CH3OH 水溶液中之計時安培法曲線圖。定電位於 0.5 V vs. Ag/AgCl。掃描時間為 1000 秒。……………………125
圖 A-1. (a)~(e)為PtW(0.06~0.14)/C450 系列電催化劑之 TEM 圖與粒徑分佈圖。……………………………………………………………………………143
圖 A-2. (a)~ (e) 為PtW(0.06~0.14)/Cs450 系列電催化劑之 TEM 圖與粒徑分佈圖。……………………………………………………………………………145
圖 A-3. (a)~ (e) 為PtW(0.06~0.14)/Cs200 系列電催化劑之 TEM 圖與粒徑分佈圖。……………………………………………………………………………147
圖 B-1. 單斜 WO3 之結晶型號 JCPDS 72-0677。……………………………148

表目錄
表 2-1.WO3 相關催化劑之整理……………………………………………………25
表 4-1.製備方法之選擇系列催化劑……………………………………………81
表 4-2.E-TEK Pt/C、Pt/C-EGR 與 Pt/Cs 電催化劑之性質參數……………90
表 5-1.PtW/Cs450 電催化劑之命名……………………………………………92
表 5-2.PtW/C450 與 PtW/Cs450 系列電催化劑之性質參數…………………102
表 5-3.PtW/C450 與 PtW/Cs450 系列電催化劑之 MOR 性質參數…………105
表 5-4.PtW/Cs200 系列電催化劑之命名 ………………………………………108
表 5-5.PtW/Cs200 系列電催化劑之性質參數…………………………………113
表 5-6.PtW/Cs200 系列電催化劑之 MOR 性質參數…………………………116
表 5-7.綜合三系列中最佳 MOR 效能電催化劑之性質參數…………………119

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