臺灣博碩士論文加值系統

近年來由於環境的退化與能源的需求量倍增相對於降低石化燃料使用等因素下，使得各國迫切採取積極的態度尋找替代性的能源，氫能於現今被認為可以做為替代石化燃料的重要能源。本研究裡，為了發展具產氫/氧、能量轉換與傳輸之雙功能光電化學電池，我們預期建構奈米複合光觸媒製程、薄膜電極體技術與表面改質技術並將所有元件與功能整合至光電化學電池中。
在本論文第一部份的研究中，主要是以製備與分析具光化學特性之二氧化錳奈米複合光觸媒材料(MnO2/MMT-clay)，並透過亞甲基藍裂解實驗對所製備之光觸媒參數與其所對應的光裂解特性進行有系統的分析與研究，企圖優化並找出最理想的製程條件。研究結果指出使用硫酸錳(MnSO4)與過硫酸銨((NH4)2S2O8)所合成出來的二氧化錳(MnO2)光觸媒具有軟錳礦和斜方錳礦結構，特別是當前驅物濃度從0.7M降低到0.1M時，軟錳礦與斜方錳礦結構之震動模態被有效提升意味著光觸媒特性被有效改善。當前驅物濃度為0.1M時於160oC燒結條件下，可以看出有很明顯的二氧化錳(MnO2)繞射峰位於2-Theta角在28.68o為B-MnO2(110)，並指出所合成的觸媒具有很好的結晶性，當前驅物濃度增加到0.7M時結晶性反而下降。若進一步將當前驅物濃度為0.1M時於160oC燒結條件下的二氧化錳(MnO2)光觸媒於亞甲基藍水溶液下進行光裂解實驗可以發現在為添加0.01g光觸媒即可產生光裂解之效果，而將單位當量提升至0.1g或1g時幾乎把亞甲基藍完全裂解，此一結果也說明並驗證此一理想之光催化特性。
本研究第二部份，即根據上述之結果，其最佳化條件將被用於雙功能光電化學電池之組裝與整合，研究結果指出在產氫效率比較下可以明顯看出Pt-MnO2/C光觸媒的產氫速率為2260umol/hr明顯大於Pt-TiO2/C光觸媒氫的產生速率為1840umol/hr，會有此明顯的差異主要歸因於甲醇水溶液在光催化過程反應中，所釋放的CO氣體毒化了TiO2觸媒上的白金粒子。在燃料電池發電過程中，極化曲線測試可以發現Pt/C/Nafion212薄膜電極體具有較大的短路電流，說明了具有較理想的疏水電極可以產生較理想的電池極化特性，特別是在低電壓高電流的條件下電極的疏水程度會影響到介面之質傳特性。其中以Pt/C/Nafion212薄膜電極體所呈現的最大輸出功率2.2mW/cm2，對應電流約為11.2 mA/cm2；在光電化電池方面，極化曲線測試結果同樣可以發現光裂解水產氫(氫氧分離)的過程電極表面能扮演的角色格外重要。以Pt-B-MnO2/C/Nafion212薄膜電極體來說因它具有較低的接觸角(高的表面能)，所以在進行質傳過程中具有低的質傳阻抗，因此非常適合應用於光電化學電池電極。Pt-B-MnO2/C/Nafion212薄膜電極體所呈現的最大輸出功率2.93mW/cm2，對應電流為14.78mA/cm2。

Hydrogen is now considered as a charming alternative to fossil fuels. Since the environmental degradation problem and increased energy demand while reducing the fossil energy are forcing various countries to take an aggressive stance for environmental friendly alternative power source. In this study, in order to develop the bi-functional photoelectrochemical cell assembly with hydrogen/oxygen generation, we propose to establish the nano-complex photocatalyst process, MEA technology, surface modified technology, and then combine all components in photoelectrochemical cell.
In first part, we propose to prepare the nano-complex MnO2 photocatalytic materials with photochemical properties and evaluate the decomposition characteristics of methylene blue in an aqueous solution under visible light irradiation in order to find the optimal prepared conditions. It is indicated that the MnO2 photocatalyst prepared with precursor of MnSO4 and (NH4)2S2O8 contains the of Pyrolusite and Ramsdellite structure. In particular, the vibration mode of the Pyrolusite and Ramsdellite structure are enhanced as precursor concentration decrease from 0.7M to 0.1M. When MnO2 prepared with precursor concentration of 0.1M under annealing temperature of 160oC, it can clearly find the diffraction profile at 2 theta of 28.68o corresponding to the B-MnO2 (110)crystalline phase as compared to the MnO2 with 0.7M prescription prepared. To further evaluate the decomposition characteristics of methylene blue in an aqueous solution under the visible light irradiation, it can be found the significant characteristics of decomposition as the introduction of 0.01g MnO2 photocatalyst.
In second part, based on above discussion, the optimal condition is proposed to fabrication and integration for establishing bi-functional photoelectrochemical cell. It is found that the hydrogen generation (2260 umol/hr) of Pt-MnO2/C MEA is larger than Pt-TiO2/C MEA (1840 umol/hr), which can ascribe to the easily CO poisoning effect for Pt-TiO2/C MEA case when electrode working in MeOH environment. For PEM fuel cell test, the MEA without photocatalyst (Pt/C/Nafion 212) have maximum short-circuit current than others, and indicating the optimal hydrophobic properties and mass transfer properties of Pt/C electrode. The maximum output power is 2.2mW/cm2 corresponding to the current density of 11.2 mA/cm2. For photoelectrochemical cell test, the MEA with containing hydrophilicity and high surface energy can provide low mass transfer resistance (e.g. Pt-B-MnO2/C/ Nafion 212 MEA). Under the visible light irradiation, Pt-B-MnO2 /C/ Nafion 212 MEA show the maximum power density of 2.93 mW/cm2 corresponding to the current density of 14.78 mA/cm2.

誌謝.......................................................I
摘要......................................................II
Abstract..................................................IV
目次......................................................VI
圖目次....................................................IX
表目次...................................................XII
第一章 序論.................................................1
1-1 前言..................................................1
1-2 文獻回顧與研究目的......................................2
第二章 二氧化錳奈米複合光觸媒材料(MnO2/MMT-clay)製備與特性研究..5
2-1 文獻回顧...............................................5
2-2 實驗..................................................9
2-2-1 實驗目的............................................9
2-2-2 實驗步驟............................................9
A.合成MnO2/clay光觸媒....................................9
B.MnO2/clay光觸媒光催化降解亞甲基藍.......................12
2-2-3 分析儀器...........................................14
A.X-射線粉末繞射分析儀(XRD)..............................14
B.掃描式電子顯微鏡分析儀(SEM)............................14
C.傅立葉轉換紅外線分光光度計(FT-IR).......................15
D.紫外光∕可見光光譜儀(UV-Visible)........................15
2-3 結果與討論............................................17
2-3-1 前驅物濃度對MnO2/clay光觸媒之影響....................17
A.不同前驅物濃度比例對MnxO2-X觸媒之化學劑量比之關係.........17
B.不同前驅物濃度比例對MnO2觸媒之結構變化...................18
2-3-2 退火溫度對MnO2/clay光觸媒晶體結構轉變之影響...........21
2-3-3 MnO2/clay光觸媒對於亞甲基藍光催化降解之研究...........24
2-4 結論.................................................30
第三章 光電化學燃料電池組裝與特性分析.........................31
3-1 文獻回顧..............................................31
A.MnO2觸媒與碳黑載體.....................................31
B.燃料電池技術...........................................32
C.光電化學產氫技術........................................37
3-2 實驗.................................................40
3-2-1 實驗步驟...........................................40
A.合成MnO2/C光觸媒......................................40
B.合成Pt/C、Pt-MnO2/C、Pt-B-MnO2/C、Pt-TiO2/C觸媒.......42
C.組裝電池..............................................44
3-2-2 分析儀器...........................................47
A.X-射線粉末繞射分析儀(XRD)..............................47
B.掃描式電子顯微鏡分析儀(SEM)............................47
C.電化學分析儀(CV)......................................48
D.氣相層析儀(GC)........................................48
E.光致激發光光譜儀(PL)...................................49
F.接觸角分析儀(CA)......................................49
G.燃料電池測試系統(I-V)..................................50
3-3 結果與討論............................................52
3-3-1 Anatase和Rutile晶體結構之二氧化鈦(TiO2)與複合相之二氧化錳(MnO2)特性與產氫效率比較..........................52
A.X光繞射分析...........................................52
B.掃描式電子顯微鏡分析...................................54
C.電化學分析............................................58
D.光觸媒裂解水產氫分析...................................61
3-3-2 Anatase和Rutile晶體結構之二氧化鈦(TiO2)與B-MnO2光電化學電池性能測試與比較..................................68
A.X光繞射分析...........................................68
B.光致激發光光譜分析.....................................70
C.光觸媒裂解水產氫分析...................................72
D.接觸角分析............................................75
E.燃料電池測試分析.......................................77
F.光電化學電池測試分析...................................79
3-4 結論.................................................81
第四章 總結................................................83
參考文獻...................................................85

[1]. 許寧逸和顏溪成，“由碳能朝向氫能的燃料電池”，科學發展，367期 (2003) 6-11.
[2]. 張嘉修，“生質氫能”，科學發展，433期 (2009) 32-35.
[3]. 王智薇，“淺談新興能源科技產業-氫能與燃料電池”，產經資訊，61 (2008) 25-29.
[4]. 黃鎮江，“燃料電池”，全華科技圖書股份有限公司，(2005).
[5]. A. Fujishima and K. Honda, Nature, 238 (1972) 37-38.
[6]. 陳東煌和莊浩宇，“光電化學反應”，化學專刊，3期 (2009) 1-8.
[7]. S. Lee, B. Choi, N. Hamasuna, C. Fushimi and A. Tsutsumi, J. Power Sources, 181 (2008) 177-181.
[8]. 陳淳圓，官文惠和黃富昌，“不同外加輔助能量形式對二氧化錳處理亞甲基藍染料廢水之影響”，台灣環境資源永續發展研討會，(2009).
[9]. F. Cheng, J. Zhao, W. Song, C. Li, H. Ma, J. Chen and P. Shen, Inorg. Chem., 45 (5) (2006) 2038-2044.
[10]. J. Ni, W. Lu, L. Zhang, B. Yue, X. Shang and Y. Lv, J. Phys. Chem. C, 113 (2009) 54-60.
[11]. T. Gao, H. Fjellvag and P. Norby, Nanotechnology, 20 (2009) 055610(7pp).
[12]. Z. He, J. Chen, D. Liu, H. Tang, W. Deng and Y. Kuang, Mater. Chem. Phys., 85 (2004) 396-401.
[13]. K. Kortsdottir, R. W. Lindstrom, T. Akermark and G. Lindbergh, Electrochim. Acta, 55 (2010) 7643-7651.
[14]. 紀景發，“以混合碳材為PtRu/C 觸媒擔體用於改良直接甲醇燃料電池中陽極觸媒層之效能”，國立成功大學化學工程學系碩士論文，(2006).
[15]. J. Cheng, H. Zhanga, H. Maa, H. Zhonga and Y. Zou, Electrochim. Acta, 55 (2010) 1855-1861.
[16]. K. T. Jeng, Y. C. Liu, Y. F. Leu, Y. Z. Zeng, J. C. Chung and T. Y. Wei, Int. J. Hydrog. Energy, 35 (2010) 10890-10897.
[17]. 鍾心怡，王瑞琪和陳樹人，“ Ag/ZnO異質結構之製備與光催化特性分析”，工程科技與教育學刊，2期 7卷 (2010) 170-176.
[18]. T. Gao, H. Fjellvag and P. Norby, Nanotechnology, 20 (2009) 5561-5568.
[19]. S. Lee, B. Choi, N. Hamasuna, C. Fushimi and A. Tsutsumi, J. Power Sources, 181 (2008) 177-181.
[20]. 蘇佳琪和申永輝，“非離子界面活性劑吸附對黏土懸浮液流變與表面性質之影響”，中國礦治工程學會，3期 52卷 (2007) 31-39.
[21]. H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard and J. M. Herrmann, Appl. Catal. B-Environ., 39 (2002) 75-90.
[22]. 沈祐豪，“利用不同觸媒催化亞甲基藍濕式氧化反應之研究”， 嘉南藥理科技大學環境工程與科學系碩士論文，(2009).
[23]. C. M. Julien, M. Massotb and C. Poinsignon, Spectroc. Acta Pt. A- Molec. Biomolec. Spectr., 60 (2004) 689-700.
[24]. G. A. Klein, Industrial Color Physics, (2010) 45-48.
[25]. P. Zoltowski, D. M. Drazic and J. Vorkapic, J. Appl. Electrochem., 3 (4) (1973) 271-283.
[26]. M. Chatenet, F.Micoud, I. Roche, E. Chainet and J. Vondrak, Electrochim. Acta, 51 (2006) 5452.
[27]. M. Baldi, V. S. Escribano, J. M. G. Amores, F. Milella and G. Busca, Appl. Catal. B-Environ., 17 (1998) 175.
[28]. D. B. Broughton and R. L. Wentworth, J. Am. Chem. Soc., 69 (1947) 741.
[29]. L. L. Bircumshaw and B. H. Newman, Proc. R. Soc. London., Ser. A., 227 (1954) 115.
[30]. A. K. Galwey and P. W. M. Jacobs, J. Chem. Soc. Faraday Trans., 55 (1959) 1165.
[31]. F. Tingming, L. Feiquan, L. Lin, G. Liwei and L. Fengsheng, Catal. Commun., 10 (2008) 108.
[32]. A. Taguchi and F. Schuth, Microporous Mesoporous Mat., 77 (2005) 1.
[33]. Y. Rao and D. M. Antonelli, J. Mater. Chem., 19 (2009) 1937.
[34]. Y. Ren, P. G. Bruce and Z. Ma, J. Mater. Chem., 21 (2011) 9312.
[35]. Y. Ren, Z. Ma, L. Qian, S. Dai, H. He and P. G. Bruce, Catal. Lett., 131 (2009) 146.
[36]. R. Gilbert and P. W. M. Jacobs, Can. J. Chem., 49 (1971) 2827.
[37]. T. Grzybek, J. Pasel and H. Papp, Phys. Chem. Chem. Phys., 1 (1999) 341.
[38]. 馬登科，“鋰離子電池支撐式碳用電極材料之製備研究”，國立中山大學化學研究所碩士論文，(2000).
[39]. 葛笑蘭和張振新，“催化動力學光度法測定衡量及機制探討”，中國食品衛生雜志，4期 22卷 (2010) 326-328.
[40]. R. Mosdale, G. Gebel and M. Pineri, J. Membr. Sci., 118 (1996) 269-277.
[41]. T. R. Ralph, G. A. Hards, J. E. Keating, S. A. Campbell, D. P. Wilkinson, M. Davis, J. S, Pierre and M. C. Johnson, J. Electrochem. Soc., 144 (1997) 11.
[42]. S. J. Lee, S. Mukerjee, J. McBreen, Y. W. Rho, Y. T. Kho and T. H. Lee, Electrochim. Acta, 43 (1998) 24 3693-3701.
[43]. D. Singh, D.M. Lu and N. Djilali, Int. J. Eng. Sci., 37 (1999) 431-452.
[44]. R. F. Mann, J. C. Amphlett, M. A.I. Hooper, H. M. Jensen, B. A. Peppley and P. R. Roberge, J. Power Sources, 86 (2000) 173-180.
[45]. S. D. Thompson, L. R. Jordan and M. Forsyth, Electrochim. Acta, 46 (2001) 1657-1663.
[46]. N. Djilali and D. Lu, Int. J. Therm. Sci., 41 (2002) 29-40.
[47]. Hsin-Sen Chu, Chung Yeh and Falin Chen, J. Power Sources, 123 (2003) 1-9.
[48]. M. Gil, X. Ji, X. Li, H. Na, J. E. Hampsey and Y. Lu, J. Membr. Sci., 234 (2004) 75-81.
[49]. P. J. Ferreira, G. J. la O, Y. S. Horn, D. Morgan, R. Makharia, S. Kocha and H. A. Gasteiger, J. Electrochem. Soc., 152 (2005) 11 2256-2271.
[50]. H. Ghassemi, J. E. McGrath and T. A. Z. Jr, Polymer, 47 (2006) 4132-4139.
[51]. I. Nitta, T. Hottinenb, O. Himanen and M. Mikkola, J. Power Sources, 171 (2007) 26-36.
[52]. N. Patel, R. Fernandes, G. Guella, A. Kale, A. Miotello, B. Patton and C. Zanchetta, J. Phys. Chem. C, 112 (2008) 6968-6976.
[53]. Z. Zhenzhong, C. Junxun and P. Ronggui, Chin. J. Chem. Eng., 17 (2) (2009) 298-303.
[54]. D.Wang, C. V. Subban, H. Wang, E. Rus, F. J. DiSalvo and H. D. Abruna, J. Am. Chem. Soc., 132 (2010) 10218-10220.
[55]. S. W. Perng and H. W. Wu, Appl. Energy, 88 (2011) 52-67.
[56]. D. Ergun, Y. Devrim, N. Bac and I. Eroglu, J. Appl. Polym. Sci., 124 (2012) E267-E277.
[57]. 莊浩宇和陳東煌，“取之不盡的太陽能光電化學反應”，科學發展，437期 (2009) 58-63.
[58]. M. Matsuoka, A. Ebrahimi, M. Nakagawa, T.-H. Kim, M. Kitano, M. Takeuchi and M. Anpo, Res. Chem. Intermed., 35 (2009) 997-1004.
[59]. 吳明珠和科以侃，“儀器分析”，新文京開發出版股份有限公司，(2008) 24-47.
[60]. 謝嘉民，賴一凡，林永昌和枋志堯，“光激發螢光量測的原理、架構及應用”，奈米通訊，2期 12卷 (2005) 28-39.
[61]. M. S. El-Deab, Int. J. Electrochem. Sci., 4 (2009) 1329-1338.
[62]. X. Zhang and K. Y. Chan, Chem. Mat., 15 (2003) 451-459.
[63]. N. A. M. Barakat, K. D. Woo, S. G. Ansaru, J. A. Ko, M. A. Kanjwal and H. Y. Kim, Appl. Phys. A, 95 (2009) 769-776.
[64]. L. Song, S. Zhang, X. Wu and Q. Wei, Chem. Eng. J., 187 (2012) 385-390.
[65]. K. Iijima, M. Goto, S. Enomoto, H. Kunugita, K. Ema, M. Tsukamoto, N. Ichikawa and H. Sakama, J. Lumines., 128 (2008) 911-913.