直接甲醇燃料電池(Direct methanol fuel cell, DMFC)具有很好的發展潛力，因為它具有高能量轉換效率和低環境影響之優勢，但陽極電催化劑的活性不高，阻礙了 DMFC 的發展。一般使用 Pt當作甲醇氧化反應(Methanol oxidation reaction, MOR)的電催化劑。然而在 MOR 的過程中會產生 CO ，它會吸附在 Pt 表面且不易移除，使得 Pt無法繼續催化MOR，稱為 CO 毒化現象。本研究使用的電催化劑以碳黑為載體，將 Pt和TiO2的奈米複合材料負載在載體上(Pt-TiO2/C)，以利於提升 MOR 效能和抵抗 CO 毒化的能力。
Pt-TiO2/C 電催化劑使用兩步法合成。第一步，使用 NaOH 處理過後的碳黑當作載體，再以溶膠/凝膠法製作 TiO2 奈米顆粒，將其負載在載體上，可以得到 TiO2/C 奈米複合材料。第二步，將 Pt 奈米顆粒負載在 TiO2/C 的表面上，即可得到 Pt-TiO2/C 電催化劑。TiO2 奈米顆粒是經由四異丙烷氧化鈦(titanium tetra-isopropoxide, TTIP) 加入含有丙酮和碘的乙醇中，發生水解與縮合反應製備而得。Pt 奈米顆粒是使用多元醇還原法所合成的，利用乙二醇當作還原劑，在酸性或鹼性的環境下進行還原反應而得。將所得的 Pt-TiO2/C 電催化劑經由穿透式電子顯微鏡 (transmission electron microscope, TEM)、X 光能譜分析儀 (energy dispersive X-ray spectrometer, EDS)、傅立葉轉換紅外線吸收光譜儀(Fourier transform infrared spectroscopy , FT-IR) 和X光繞射分析儀 (X-ray diffractometer, XRD) 去分析其特性，並使用循環伏安法 (cyclic voltammetry, CV) 和計時安培法 (chronoamperometry, CA) 進行 MOR 效能、電化學活性表面積 (electrochemical active surface area, EASA)、CO 脫附與穩定性等電化學特性分析。
Pt-TiO2/CS(2)(80, 200, 450)A 和 Pt-TiO2/C(2)(80, 200, 450)A 兩系列電催化劑是在酸性環境下，利用 NaOH 處理過或未經處理的碳黑當作載體，並使用不同的燒結溫度所製作而成。Pt 奈米顆粒大小大約在 5~8 奈米且有聚集的現象。Pt-TiO2/CS(2)(200, 450, 600)B 和 Pt-TiO2/C(2)(200, 450, 600)B 兩系列的電催化劑是在鹼性環境下所製作的。Pt 奈米顆粒大小大約在 2~4 奈米且均勻分散在載體上，而且他們的 MOR 效能有明顯的提升。所以 Pt-TiO2/CS(1-5)450B 系列的電催化劑選擇在鹼性環境下製作，並改變 TiO2 和 C 的組成，找出最好的 MOR 效能。結果顯示 Pt-TiO2/CS(1-5)450B 系列電催化劑的 MOR 效能均高於市售 E-TEK Pt/C。Pt-TiO2/CS(4)450B 可以得到最好的 MOR 效能 799 ± 62 A/g-Pt，大約為市售 E-TEK Pt/C 414 ± 59 A/g-Pt 的 1.93 倍。

Direct methanol fuel cell (DMFC) has been considered as a new potential energy source in the near future owning to its higher energy conversion efficiency and smaller environmental impact compared to conventional fossil-based energy generation systems. However, the low activity of the anode electrocatalysts is one of the major problems for the development of DMFC. Pt is widely used as the electrocatalyst for methanol oxidation reaction (MOR). However, Pt can be easily poisoned by the strongly adsorbed intermediates generated during MOR, such as CO, and lose its electrocatalytic activity rapidly. In this study, Pt-TiO2 nanocomposites supported on carbon black was used as the electrocatalyst, in order to enhance the MOR efficiency and CO-tolerance ability.
The Pt-TiO2/C electrocatalysts were prepared by two-step procedure. First step, XC-72 was pretreated with NaOH aqueous solution and decorated with solgel-derived TiO2 nanoparticles to get TiO2/C as the substrate. Second step, Pt nanoparticles were prepared onto the substrate surface to obtain Pt-TiO2/C electrocatalysts . The TiO2 nanoparticles were synthesized by catalyzed hydrolysis and inhibited condensation reaction of titanium tetra-isopropoxide in an ethanol solution containing acetone and Iodine. A polyol process using ethylene glycol as the reducing agent was employed at acidic or basic condition for the synthesis of the Pt nanoparticles. The resultant Pt-TiO2/C electrocatalysts have been characterized by means of transmission electron microscope  (TEM), energy dispersive X-ray spectrometer (EDS), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffractometer (XRD) analysis. 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 acidic polyol condition, the Pt-TiO2/CS(2)(80, 200, 450)A and Pt-TiO2/C(2)(80, 200, 450)A series electrocatalysts used NaOH-pretreated and pristine Vulcan XC-72 carbon black as the support and annealed at different temperature, the Pt nanoparticle aggregates with sizes of 5~8 nm were obtained. For the basic polyol condition (Pt-TiO2/CS(2)(200, 450, 600)B and Pt-TiO2/C(2)(200, 450, 600)B series), the Pt nanoparticle uniformly dispersed with sizes of 2~4 nm were obtained, and their MOR efficiency were sighificantly improve. In order to optimize  the composition of  TiO2 and Vulcan XC-72 carbon, the Pt-TiO2/CS(1-5)450B series electrocatalyst were synthesized using NaOH-pretreated Vulcan XC-72 carbon black and calcined at 450oC. The MOR efficiency of these electrocatalysts were all higher than the commercial E-TEK Pt/C electrocatalyst. The Pt-TiO2/CS(4)450B electrocatalyst achieved the highest MOR efficiency of 799 ± 62 A/g-Pt among all the electrocatalysts prepared in this study, and which was about 1.93 times higher than that of the commercial E-TEK Pt/C electrocatalyst (414 ± 59 A/g-Pt).

目錄
中文摘要	I
英文摘要	III
圖目錄	IX
表目錄	XII
第一章	緒論	1
1.1 前言	1
1.2 燃料電池的種類	3
1.3直接甲醇燃料電池	4
1.4	DMFC之陽極電催化劑	6
1.4.1雙元合金電催化劑	6
1.4.2鉑-過渡金屬氧化物之電催化劑	7
1.5	研究目的與動機	8
第二章 文獻回顧	9
2.1 Pt/TiO2 和 Pt-TiO2/C 應用於氧氣還原反應	9
2.2 以 TiO2 為載體之 Pt-TiO2 電催化劑	14
2.3以 TiO2/C 為載體之電催化劑	20
第三章 實驗	24
3.1 研究目的與方法	24
3.2 實驗架構	25
3.3 實驗步驟	26
3.3.1 碳載體之前處理	26
3.3.2 TiO2 奈米顆粒之製備步驟	26
3.3.3 TiO2 奈米複合顆粒製備之方法	26
3.3.4 Pt-TiO2/C 電催化劑之製備	26
3.4 表面型態與性質分析	28
3.4.1 表面能量散射X光光譜儀(energy dispersive X-ray spectroscopy, EDS)	28
3.4.2 X 光繞射分析儀 (X-ray diffractometer, XRD)	28
3.4.3 穿透式電子顯微鏡 (transmission electron microscope, TEM)	28
3.4.4 傅立葉轉換紅外線吸收光譜儀 (Fourier Transform Infrared Spectroscopy, FTIR)	28
3.5 電化學分析	29
3.5.1 循環伏安法 (Cyclic voltammetry, CV)	29
3.5.2 計時安培法 (Chronoamperometry, CA)	33
3.6 實驗藥品及設備	34
第四章 TiO2/C 奈米複合顆粒之製備與性質分析	35
4.1 TiO2/C 奈米複合顆粒之影響	35
4.2 表面型態與元素分析	37
4.3 燒結溫度與TiO2/C奈米複合顆粒結晶性質	42
第五章 Pt-TiO2/C 電催化劑 MOR 效能最佳化	49
5.1 酸性環境下碳載體與燒結溫度之影響	49
5.1.1 EDS 元素分析	50
5.1.2 TEM 表面形態與結構分析	51
5.1.3 XRD 晶型結構分析	54
5.1.3 電催化劑之 MOR 效能	56
5.2 鹼性環境下碳載體與燒結溫度之影響	60
5.2.1 EDS 元素分析	61
5.2.2 TEM 表面形態與結構分析	62
5.2.3 XRD 晶型結構分析	65
5.2.4 電催化劑之 MOR 效能	66
5.3 Pt/Ti比例對於電催化劑之影響	70
5.3.1 EDS 元素分析	71
5.3.2 TEM 表面形態與結構分析	73
5.3.3 XRD 晶型結構分析	76
5.3.4 電催化劑之 MOR 效能	77
5.4 電催化劑效能比較	81
5.4.1CO脫附能力測試 和穩定性之比較	82
第六章 結論	85
建議	87
參考文獻	88
圖目錄
圖 1-1. DMFC工作原理。…………………………………….4
圖 1-2.鉑-過渡金屬氧化物之催化劑示意圖。…………………………………….7
圖 2-1. XRD pattern of Pt/TiO2 after annealing at 300 °C for 2 h in argon gas atmosphere. * corresponds to the rutile phase. 54……………………………….10
圖 2-2. TEM images of (a) TiO2 and (b) Pt/TiO2. 54………………………………...10
圖 2-3. Transmission electron micrographs of (a) titania support, (b) 20 wt% Pt/TiO2, and (b) 60 wt% Pt/TiO2 electrocatalyst. 74……………………………………..11
圖 2-4. XRD patterns of (a) Pt/C and (b) Pt/TiO2/C catalyst. 43…………………….12
圖 2-5. TEM images of the catalysts: Pt/C catalyst (a) before CV; (b) after CV; Pt/TiO2/C catalyst (c) before CV; and (d) after CV. 43………………………….13
圖 2-6. (A-C) TEM image of the anatase nanofiber after its surface had been decorated with Pt nanoparticles by immersing the sample in a polyol reduction bath for 3, 7, and 19 h, respectively.52………………………………………….14
圖 2-7. (B) Chronoamperometry curves recorded at 0.85 V for various samples. The measurement condition is as follows: 0.5 M MeOH, 0.5 M H2SO4, set potential of 0.85 V (vs RHE), and pretreatment before tests at 0 V for 30 s.52…………15
圖 2-8. TEM images of TiO2 (a and b) and the Pt/TiO2 catalyst(d and e). 49………16
圖 2-9. CO stripping curves recorded in 0.5 M H2SO4 with a scan rate of 20 mV/s: Pt/TiO2 catalyst; Pt/C catalyst. 49………………………………………………16
圖 2-10. CO stripping cyclic voltammograms in a CO saturated 0.5 M H2SO4 solution. The scan rate was 20 mV/ s. 47…………………………………………………17
圖 2-11. Cyclic voltammograms of methanol electro-oxidation in the 1 MCH3OH + 1 M H2SO4 solution. The scan rate was 20 mV/s. 47……………………………18
圖 2-12. Chronoamperometry curves in the solution of 1 M CH3OH + 1 M H2SO4 at room temperature for 1 h. The oxidation potential was kept at 0.5 V vs. SCE. 47………………………………………………………………………………18
圖 2-13. a) TEM and (b) HRTEM images of the Pt–S–TiO2/CNT catalyst.37………20
圖 2-14. Cyclic voltammograms recorded in a solution containing 1M HClO4 and 1M CH3OH measured at a scan rate of 50mV/s.37…………………………………21
圖 2-15. CO stripping voltammograms recorded in 1M HClO4 solutions at a scan rate of 10mV/s.37……………………………………………………………………21
圖 3-1. Pt-TiO2/C 和 Pt-TiO2/CS 電催化劑之製備流程示意圖。…………………24
圖 3-2. 實驗架構及流程圖。………………………………………………………..25
圖 3-3. 三極式電化學實驗系統示意圖。…………………………………………..29
圖 3-4. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 + 1M CH3OH 之 CV 圖，掃描速率為 50 mV/s。………………………………………………………………..31
圖 3-5. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 水溶液中進行 CO 脫附測試之CV 圖，掃描速率為 50 mV/s。……………………………………………....31
圖 3-6. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 之 CV 圖，掃描速率為 50 mV/s。…………………………………………………………………………32
圖 3-7. E-TEK Pt/C 電催化劑於 0.5 M H2SO4 + 1M CH3OH 之 CA 曲線圖。定電位於0.5 V (vs. Ag/AgCl)，時間為 1000 秒。……………………………....33
圖 4-1. C 和 CS 碳載體之 FTIR  圖譜。……………………………………….39
圖 4-2. (a) TiO2/CS(2)80、(b) TiO2/C(2)80 和 (c) Vulcan XC-72 之 TEM 圖。…...41
圖 4-3. TiO2/CS(2) 奈米複合顆粒系列之 XRD 分析圖譜。……........... ……......43
圖 4-4. TiO2/C(2) 奈米複合顆粒系列之 XRD 分析圖譜。………………………..43
圖 4-5. (a) TiO2/CS(2)80、(b) TiO2/CS(2)450、(c) 和 (d) TiO2/CS(2)600之TEM圖。.46
圖 4-6. TiO2/CS(2)450 奈米複合顆粒 (a) TEM 圖、(b) TEM-Mapping Ti 分佈圖。. ……………………………………………………………………………47
圖 4-7. (a) TiO2/CS(2)450、(b) TiO2/CS(2)600 之高解析度 TEM 圖。……………48
圖 5-1. (a) Pt-TiO2/CS(2)80A、(b) Pt-TiO2/CS(2)200A 與 (c) Pt-TiO2/CS(2)450A 電催化劑之 TEM 圖。………………………………………………...………….52
圖 5-2. (a) Pt-TiO2/C(2)80A、(b) Pt-TiO2/C(2)200A 與 (c) Pt-TiO2/C(2)450A 電催化劑之 TEM 圖。………………………………………………………………...53
圖 5-3. Pt-TiO2/CS(2)A 和 Pt-TiO2/C(2)A 系列電催化劑之 XRD 分析圖譜。….55
圖 5-4. Pt-TiO2/CS(2)A 系列電催化劑於 (a) 0.5 M H2SO4 與 (b) 0.5 M H2SO4 + 1 M CH3OH 水溶液中之 CV 圖，掃描速率為 50 mV/s。…………………..…57
圖 5-5. Pt-TiO2/C(2)A 系列電催化劑於 (a) 0.5 M H2SO4 與 (b) 0.5 M H2SO4 + 1 M CH3OH 水溶液中之 CV 圖，掃描速率為 50 mV/s。………………….…58
圖 5-6. (a) Pt-TiO2/CS(2)200B、(b) Pt-TiO2/CS(2)450B 與 (c) Pt-TiO2/CS(2)600B 電催化劑之 TEM 圖。…………………………………………………………….63
圖 5-7. (a) Pt-TiO2/C(2)200B、(b) Pt-TiO2/C(2)450B 與 (c) Pt-TiO2/C(2)600B 電催化劑之 TEM 圖。………………………………………………………………64
圖 5-8. Pt-TiO2/CS(2)B 和 Pt-TiO2/C(2)B 系列電催化劑之 XRD 分析圖譜。….65
圖 5-9 . Pt-TiO2/CS(2)B 系列電催化劑於 (a) 0.5 M H2SO4 與 (b) 0.5 M H2SO4 + 1 M CH3OH 水溶液中之 CV 圖，掃描速率為 50 mV/s。…………………..…68
圖 5-10. Pt-TiO2/C(2)B 系列電催化劑於 (a) 0.5 M H2SO4 與 (b) 0.5 M H2SO4 + 1 M CH3OH 水溶液中之 CV 圖，掃描速率為 50 mV/s。…………………..…69
圖 5-11. (a) Pt-TiO2/CS(1)450B、(b) Pt-TiO2/CS(2)450B、(c) Pt-TiO2/CS(3)450B、(d) Pt-TiO2/CS(4)450B 與 (e) Pt-TiO2/CS(5)450B 電催化劑之 TEM 圖。….….75
圖 5-12. Pt-TiO2/CS(1-5)B系列的電催化劑之 XRD 分析圖譜。…. …. …. ….….76 
圖 5-13. Pt-TiO2/CS(1-5)B 系列電催化劑於 (a) 0.5 M H2SO4 與 (b) 0.5 M H2SO4 + 1 M CH3OH 水溶液中之 CV 圖，掃描速率為 50 mV/s。.. .. …… .. ..…..…79
圖 5-14. Pt-TiO2/CS(1-5)450B 系列的電催化劑之 Ti/(Ti+C) 真實重量百分率與 Pt/Ti 原子比和 Pt 顆粒大小與 EASA 比較圖。…………………………….80
圖 5-15. Pt-TiO2/CS(1-5)450B 系列的電催化劑之 Ti/(Ti+C) 真實重量比與 Pt/Ti 原子比和 MOR 效能比較圖。…………………………………………….….80
圖 5-16. Pt-TiO2/CS(2)450A、Pt-TiO2/C(2)80A、Pt-TiO2/CS(2)450B 、 Pt-TiO2/C(2)600B 和 Pt-TiO2/CS(4)450B 與 E-TEK Pt/C 電催化劑於飽和 CO 之 0.5 M H2SO4 水溶液之 CV 圖，掃描速率為 50 mV/s。…………………………………….83
圖 5-17. Pt-TiO2/CS(2)450A、Pt-TiO2/C(2)80A、Pt-TiO2/CS(2)450B 、 Pt-TiO2/C(2)600B、Pt-TiO2/CS(4)450B 與 E-TEK Pt/C 和 E-TEK PtRu/C 電催化劑於0.5 M H2SO4 + 1 M CH3OH 之 CA 曲線圖，定電位於 0.5 V vs. Ag/AgCl，掃描時間 1000 s，(a) 0~1000 s (b) 950~1000 s。……………….….84
圖A-1、(a) ~ (c) 為 Pt-TiO2/CS(2)A 系列電催化劑之 TEM 圖與粒徑分佈圖。....97
圖A-2、(a) ~ (c) 為 Pt-TiO2/C(2)A 系列電催化劑之 TEM 圖與粒徑分佈圖。….98
圖A-3、(a) ~ (c) 為 Pt-TiO2/CS(2)B 系列電催化劑之 TEM 圖與粒徑分佈圖。....99
圖A-4、(a) ~ (c) 為 Pt-TiO2/C(2)B 系列電催化劑之 TEM 圖與粒徑分佈圖。…100
圖A-5、(a) ~ (d) 為 Pt-TiO2/CS(1-5)B 系列電催化劑之 TEM 圖與粒徑分佈圖..102
表目錄
表 1-1. 燃料電池種類3………………………………………………………………3
表 2-1. Activity (A) and loss of oxygen reduction reaction activity (ORRloss) at 0.85V for Pt/TiO2 and Pt/C measuredafter potential cycling experiments.74………………11
表 2-2. Summary of particle size and electrochemical surface area(ECSA) measured under 0 and 2500 cycles after potential cycling between 0.6 and 1.4V for two Pt electrocatalysts.74……………………………………………………………………11
表 2-3. TiO2 相關電催化劑之整理………………………………………………23
表 4-1. TiO2/ C 奈米複合顆粒 SEM-EDS 之結果………………………….….37
表 4-2. TiO2/ C 奈米複合顆粒…………….........……………………………….....37
表 4-3. TiO2/ C 奈米複合顆粒之命名…….....………………………………….....42
表 5-1. Pt-TiO2/CS(2) A 和 Pt-TiO2/C(2) A 兩系列電催化劑之命名……….……..49
表 5-2. Pt-TiO2/CS(2)A 和 Pt-TiO2/C(2)A 兩系列電催化劑 EDS 之結果…..……50
表 5-3. Pt-TiO2/CS(2)A 和 Pt-TiO2/C(2)A 兩系列電催化劑之 Pt 平均粒徑…......51
表 5-4. Pt-TiO2/CS(2)A 和Pt-TiO2/C(2)A 兩系列電催化劑之 MOR 性質參數....59
表 5-5. Pt-TiO2/CS(2)B 和 Pt-TiO2/C(2)B 兩系列電催化劑之命名……………...60
表 5-6. Pt-TiO2/CS(2)B 和 Pt-TiO2/C(2)B 兩系列電催化劑 EDS 之結果…..……61
表 5-7. Pt-TiO2/CS(2)B 和 Pt-TiO2/C(2)B 兩系列電催化劑之 Pt 平均粒徑..62
表 5-8. Pt-TiO2/CS(2)B 和 Pt-TiO2/C(2)B 兩系列電催化劑之 MOR 性質參數…67
表 5-9. 綜合四系列 Pt-TiO2/C 電催化劑之 MOR 性質參數。….. ……………67
表 5-10. Pt-TiO2/CS(1-5)450B 系列的電催化劑之命名…..………………………70
表 5-11. TiO2/CS(1-5) 奈米複合顆粒SEM-EDS之結果……………………..……71
表 5-12. TiO2/CS(1-5) 奈米複合顆粒之性質比較……………………………..……72
表 5-13  Pt-TiO2/CS(1-5)450B 系列的電催化劑 EDS 之結果…………………72
表 5-14. Pt-TiO2/CS(1-5)450B 系列的電催化劑之 Pt平均粒徑……………..……73
表 5-15. Pt-TiO2/CS(1-5)450B 系列的電催化劑之 MOR 性質參…………..……..78
表 5-16. 綜合五系列最佳 MOR 效能電催化劑之性質參數……………..……..81

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