對於直接甲酸燃料電池而言，陽極催化劑鈀觸媒近年來引起廣泛的研究興趣。本研究利用含浸法、多元醇法及同步輻射X光合成法合成具固溶相雙金屬的金-鈀觸媒，並承載於參雜釕或銥的氧化鈰修飾過的奈米碳管載體。研究中以XRD、SEM、TEM、TGA及ICP檢測產物的組成、結構與表面形貌。
本實驗以固溶雙金屬與金屬氧化物修飾載體的觸媒，藉此期望能加強催化效能、提高導電度及避免觸媒毒化問題。實驗結果顯示：完全固溶相雙金屬的金-鈀觸媒能避免鈀金屬在電催化反應中溶出(同步輻射X光合成法)；而參雜後的氧化物並無明顯提升其導電度；添加氧化物對於觸媒毒化問題並無明顯改善。

For the direct formic acid fuel cell, Pd anode catalyst has attracted considerable attention recently. In this thesis, forming solid solution phase of Au and Pd with Ir or Ru doped CeO¬2 modified MWCNTs substrate by impregnation, polyol and synchrotron X-ray irradiation methods are studied. The composition, structure and morphology are analyzed by XRD、SEM、TEM、TGA and ICP respectively.
In this study, the catalyst of bimetal solid solution decorated on doped metal oxide modified supports in order to enhance the catalytic ability, conductivity, and prevent from the catalyst poisoning. The study firstly confirmed that completely bimetal solid solution (by X-ray irradiation method) could prevent the leaching of Pd metal in formic acid. Secondly, the doped metal oxide modified supports with catalyst did not significantly improve the conductivity. Last, addition of (doped) metal oxide did not have significant improvement in the issue of catalyst poisoning.

ABSTRACT I
摘要 II
致謝 III
TABLE OF CONTENTS IV
LIST OF TABLES VI
LIST OF FIGURES VII
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 LITERATURE REVIEW 4
2.1 Introduction of Direct Formic Acid Fuel Cells 4
2.2 Introduction of Golde Catalyst 7
2.3 Introduction of Palladium Catalyst 9
2.4 Introduction of Doping Metal of Iridium 11
2.5 Introduction of Doping Meatal of Ruthenium 14
2.6 Introduction of Ceria 16
2.7 Introduction of Carbon Nanotubes ..20
2.8 Synthesis Technology ..27
2.8.1 Impregnation Method 27
2.8.2 Polyol process 27
2.8.3 Synchrotron X-ray Irradiation Method 32
CHAPTER 3 EXPERIMENTATAION 35
3.1 Materilas 35
3.2 Sample Preparation 36
3.2.1 Acid Treatment of MWCNTs 36
3.2.2 Preparation of Metal Oxide/MWCNTs 37
3.2.3 Preparation of Pd or AuPd/(Metal Oxide)/MWCNTs 38
3.2.3.1 Polyol method 38
3.2.3.2 Synchrotron X-ray Irradiation Method 40
3.3 Specimen Analysis 41
3.3.1 Raman Scattering Spectroscopy 41
3.3.2 X-Ray Diffraction analysis 42
3.3.3 Field Emission Scanning Electron Microscope 43
3.3.4 Transmission Electron Microscopy 44
3.3.5 Thermo Gravimetric Analyzer 44
3.4 Inductively Coupled Plasma-Optical Emission Spectrometer 45
3.5 Cyclic Voltammetry Measurement 46
CHAPTER 4 RESULTS AND DISCUSSION 47
4.1 Raman Spectroscopy 47
4.2 Structure Analysis 49
4.3 FESEM 62
4.4 HRTEM 86
4.5 TGA Analysis 91
4.6 ICP-OES Analysis 92
4.7 Cyclic Voltammetry 93
CHAPTER 5 CONCLUSIONS 136
CHAPTER 6 FUTURE STUDY 140
REFERENCES 141

1.S. Ha, B. Adams, R.I. Masel. J. Power Sources 128 (2004) 119.
2.X. Yu, P.G. Pickup. J. Power Sources 182 (2008) 124.
3.X. Wang, J.M. Hu, I.M. Hsing. J. Electroanalytical Chemistry 562 (2004) 73.
4.Y.W. Rhee, S. Y. Ha, R. I. Masel. J. Power Sources 117 (2003) 35.
5.N. Hoshi, K. Kida, M. Nakamura, M. Nakada, K. Osada. J. Phys. Chem. B 110 (2006) 12480.
6.R. Larsen, J. Zakzeski, R.I. Masel. Electrochemical and Solid-State Letters 8 (2005) A291.
7.H. Lee, S.E. Habas, G.A. Somorjai, P. Yang. J. Am. Chem. Soc. 130 (2008) 5406.
8.M.H. Shao, K. Sasaki, R.R. Adzic. J. Am. Chem. Soc. 128 (2006) 3526.
9.Y.J. Chiou, K.Y. Chen, H.M. Lin, W.J. Liou, H.W. Liou, S.H. Wu, A. Mikolajczuk, M. Mazurkiewicz, A. Malolepszy, L. Stobinski, A. Borodzinski. Phys. Status Solidi A 208 No. 8 (2011) 1778.
10.M. GoE tz, H. Wendt. Electrochimica Acta 43 No. 24 (1998) 3637.
11.A.F. Diwell, R.R. Rajaram, H.A. Shaw, T.J. Truex. Catalysis and Automotive Pollution Control II (1991) 139.
12.M. Ozawa, M. Kimura. Journal of Materials Science Letters 9 (1990) 291.
13.Mazen A. Shalab. J. Chem. Tech. Biotechnol 65 (1996) 317.
14.Y. Feng, T. He, N. Alonso-Vante. Chem. Mater. 20 (2008) 26.
15.S. Litster, G. McLean. J. Power Sources 130 (2004) 61.
16.M. Mazurkiewicz, A. Małolepszy, A. Mikołajczuk, P. Kędzierzawski, L. Stobiński, K. J. Kurzydłowski, A. Borodziński. Highly Dispersed Pd/MWCNTS Catalysts For Electrooxidation of Formic Acid in Direct fuel Cells.
17.W. Li, X. Wang, Z. Chen, M. Waje, Y. Yan J. Phys. Chem. B 110 (2006) 15353.
18.C. Lamy, S Rousseau, E. M. Belgsir, C. Coutanceau, J.M Leger, Electrochim. Acta 49 (2004) 3901.
19.R. Larsen, S. Ha, J. Zakzeski, R.I. Masel, J. Power Sources 157 (2006) 78.
20.J.H. Yu, H. G. Choi, S. M. Cho, Electrochem. Comm. 7 (2005) 1385.
21.C. Rice, S. Ha, R.I. Masel, P. Waszczuk, A. Wieckowski, T. Barnard. Journal of Power Sources 111 (2002) 83.
22.“ gold ” Encyclopedia Britannica from Encyclopedia Britannica 2007 Ultimate
Reference Suite.
23.“ gold catalyst ” http://www.scopus.com/scopus/home.url, Elsevier B.V. (2008).
24.M. Haruta. Catal. Today 36 (1997) 153.
25.M. Haruta, N. Yamada, T. Kobayashi, S Iijima, J. Catal. 115 (1989) 301.
26.H. Tsunoyama, H. Sakurai, Y. Negishi, and T. Tsukuda. J. Am. Chem. Soc. 127 (2005) 9374.
27.A. Luengnaruemitchai, S. Osuwan, E. Gulari. Catal Commun. (2003) 215.
28.T. Sasaki, N. Koshizaki, M. Koinuma, Y. Matsumoto. Nanostruct. Mater. 12 (1999) 511.
29.M. Okumura, S. Nakamura, S. Tsubota, T. Nakamura, M. Azuma, M. Haruta. Catal. Lett. 51 (1998) 53.
30.J.M.C. Soares, P. Morrall, A. Crossley, P. Harris, M. Bowker, J. Catal. 219 (2003) 17.
31.Y. Yuan, A. P. Kozlova, K. Asakura, H. Wan, K. Tsai, Y. Iwasawa, J. Catal. 170 (1997) 191.
32.G. R. Bamwenda, S. Tsubota, T. Nakamura, M. Haruta. Catal. Lett. 44 (1997) 83.
33.J. M.C. Soares, M. Bowker, Appl. Catal. A: Gen. 291 (2005) 136.
34.S. Arrii, F. Morfin, A. J. Renouprez, J. L. Rousset. J. Am. Chem. Soc. 126 (2004) 1199.
35.J.D. Grunwaldt, C. Kiener, C. Wogerbauer, A. Baiker. J. Catal. 181 (1999) 223.
36.D. Guillemot, V. Yu. Borovkov, V. B. Kazansky, M. Polisset–Thfoin, J. Fraissarda. J. Chem. Soc. Faraday Trans. 93 (1997) 3587.
37.B. K. Min, W. T. Wallace, D. W. Goodman. J. Phys. Chem. B 108 (2004) 14609.
38.N. Lopez, J.K. Norskov, T.V.W. Janssens, A. Carlsson, A. Puig–Molina, B.S. Clausen, J.D. Grunwaldt. J. Catal. 225 (2004) 86.
39.B. K. Min, W. T. Wallace, A. K. Santra, D. W. Goodman. J. Phys. Chem. B 108 (2004) 16339.
40.J. L. Margitfalvi, M. Hegedus, A. Szegedi, I. Sajo, Appl. Catal. A: Gen. 272 (2004) 87.
41.K. Qian, Z. Jiang, W. Huang. J. Mol. Catal. A: Chem. 264 (2007) 26.
42.A. K. Tripathi, V. S. Kamble, N. M. Gupta. J. Catal. 187 (1999) 332.
43.U. R Pillai, S. Deevi. Appl. Catal. A: Gen. 299 (2006) 266.
44.W.C. Li, M. Comotti, F. Schuth. J. Catal. 237 (2006) 190.
45.D.T Thompson. Chemistry in Britain. 37 (2001) 43.
46.D.T. Thompson, C.W. Corti and R.J. Holliday. ATT Congress, Paris, July 2002, Paper 2002-01-2148.
47.Y. Li, X. M. Hong, D. M. Collard, M. A. El-Sayed. Org. Lett. 2 (2000) 2385.
48.S.W. Kim, J. Park, Y. Jang, Y. Chung, S. Hwang, T. Hyeon. Nano Lett. 3 (2003) 1289.
49.A. Nemamcha, J.L. Rehspringer, D. Khatm. Phys. Chem. B 110 (2006) 383.
50.L.B. Hunt. Platinum Metals Review 31 (1987) 32.
51.V. Kumar, D. Selvanathan, A. Kuliev, S. Kim, J. Flynn, I. Adesida. Electronics Letters 39 (2003) 747.
52.T. Ioroi, K. Yasuda. J. Electrochemical Society 152 (2005) A1917.
53.Y. Zhang, C. Wang, N. Wan, Z. Mao. Int. J. Hydrogen Energy 32 (2007) 400.
54.W. Yao, J. Yang, J. Wang, Y. Nuli. Electrochemistry Communications 9 (2007) 1029.
55.Y. Takasu, N. Yoshinaga, W. Sugimoto. Electrochemistry Communications 10 (2008) 668.
56.A. Hamnett, B. J. Kennedy. Electrochimica Acta 33 (1988) 1613.
57.H. Tsaprailis, V. I. Birss. Electrochem. Solid-State Lett. 7 (2004) A348.
58.R. Gomez, M. J. Weavrz. Langmuir 14 (1998) 2525.
59.C. Tang, S. Zou, M. W. Severson, M. J. Weaver. J. Phys. Chem. B 102 (1998) 8546.
60.R. Gomez, M. J. Weaver. J. Phys. Chem. B 102 (1998) 3754.
61.L.B. Hunt, F.M. Lever. Platinum Metals Review 13 (1969) 126.
62.C. Rao. Coordination Chemistry Reviews 249 (2005) 613.
63.R.W. Schutz. Platinum Metals Review 40 (1996) 54.
64.B.C.H. Steele, A. Heinzel. Nature 414 (2001) 345.
65.J. A. T. Norman, D. A. Robert, A. K. Hochberg. Thin Solid Films. 262 (1995) 46.
66.K. G. Caulton, M. H. Chisholm, S. R. Drake, W. E. Streib. Angew. Chem. Int. Ed. Engl. 29 (1990) 1483.
67.W. F. Lin, M. S. Zei, M. Eiswirth, G. Ertl, T. Iwasita, W. Vielstich. J. Phys. Chem. B 103 (1999) 6968.
68.J. W. Long, R. M. Stroud, K. E. Swider-Lyons, D. R. Rolison. J. Phys. Chem. B 104 (2000) 9772.
69.Z. Liu, J. Y. Lee, M. Han, W. Chen, L. M. Gan. J. Mater. Chem. 12 (2002) 2453.
70.吳宗昆，「於陶瓷纖維上合成Au/CeO2並進行苯及甲苯的完全氧化反應之研究」，國立中央大學化學工程與材料工程研究所碩士論文，2007年6月.
71.S. Deshpande, S. Patil, S. Kuchibhatla, S. Sea. Appl. Phys. Lett, 87 (2005) 133113.
72.M. Ricken, J. Nolting, I. Riess. J. Solid State Chem. 54 (1984) 89.
73.R. Korner, M. Ricken, J. Nolting, I. Riess. J. Solid State Chem. 78 (1989) 136.
74.O.T. Sgrensen. Non Stoichiometric Oxides, Academic Press, New York, 1981.
75.A. Laachir, V. Perrichon, A. Badri, J. Lamotte, E. Catherine, J. C. Lavalley, J. E. Fallah, L. Hilaire, F. Le Normand, E. QutmCrC, G. N. Sauvion, O. Touret. J. Chem. SOC. Faraday Trans. 87 (1991) 1601.
76.A. Badri, J. Lamotte, J. C. Lavalley, A. Laachir, V. Perrichon, O. Touret, G. N. Sauvion, and E. Quemere, Eur. J. Solid State Inorg. Chem. 28 (1991) 445.
77.K.C. Taylor. Catal. Rev.Sci. Eng. 35 (1993) 457.
78.A. Trovarelli. Catal. Rev. 38 (1996) 439.
79.T. X. T. Sayle, S. C. Parker, C. R. A. Catlow. J. Chem. Soc. Commun. 14 (1992) 977.
80.W. Chu, H. Windawi. Chem. Eng. Prog. (1996) 37.
81.R.K. Usmen, G.W. Graham, W.L.H. Watkins, R.W. McCabe. Catal. Lett. 30 (1995) 53.
82.J.C. Frost, Nature. 334 (1988) 577.
83.S.E. Golunski, H.A. Hatcher, R.R. Rajaram, T.J. Truex. Appl. Catal. B:Environ. 5 (1995) 367.
84.S. Scire, S. Minico, C. Crisafulli, C. Satriano, A. Pistone. Appl. Catal. B:Environ. 40 (2003) 43.
85.http://www.nanotubeseu.com/
86.M. Dresselhaus, G. Dresselhaus, P. Avouris. Carbon Nanotubes: Synthesis, Structure, Properties, and Applications. Springer, 2001.
87.P. J. F. Harris. Carbon Nanotubes and Realted Structures. Cambridge University Press, 1999.
88.S. Reich, C. Thomsen, and J. Maultzsch. Carbon Nanotubes. WILEY-VCH, first reprint edition, 2004.
89.A. Moisala, A. G. Nasibulin, E. I. Kauppinen. J. Physics: Condensed Matter 15 (2003) 3011.
90.H. Dai. Surface Science 500 (2002) 218.
91.R. G. Lacerda, A. S. Teh, M. H. Yang, K. B. K. Teo, N. L. Rupesinghe, S. H. Dalal, K. K. K. Koziol, D. Roy, G. A. J. Amaratunga, W. I. Milne, M. Chhowalla, D. G. Hasko, F. Wyczisk, and P. Legagneux. Applied Physics Letters 84 (2004) 269.
92.J. Kong, H. T Soh, A. M. Cassel, C. F. Quate, H. Dai. Nature 395 (1998) 878.
93.I. Radu, Y. Hanein, D. H. Cobden. Nanotechnology 15 (2004) 473.
94.H. Cui, G. Eres, J. Y. Howe, A. Puretkzy, M. Varela, D. B. Geohegan, D. H. Lowndes. Chemical Physics Letters 374 (2003) 222.
95.S. Iijima. Physica B 323 (2002) 1.
96.J. B. Nagy, G. Bister, A. Fonseca, D. Mehn, Z. Konya, I. Kiricsi, Z. E. Horvath, and L. P. Biro. J. Nanoscience and Nanotechnology 4 (2004) 326.
97.M. Terrones. Annual review of materials research 33 (2003) 419.
98.P. G. Collins, P. Avouris. Scientific American 283 (2000) 62.
99.羅吉宗、戴明鳳、林鴻明、鄭振宗、蘇程裕、吳育民, “奈米科技導論”, 2008.
100.C. Miko, L. Forro. Synthesis, Characterization and Macroscopic Manipulation of Carbon Nanotubes. Lausanne, EPFL, 2005.
101.Furer, Jurg. Growth of single-wall carbon nanotubes by chemical vapor deposition for electrical devices. Basel, 2006.
102.董慕凱，陳郁文。科學發展2005年6月，390期
103.K. B. J. Acres, A. J. Bird, J. W. Jenkins, F. King. Spec. Period. Rep. Catal. 4 (1981) 1.
104.http://en.wikipedia.org/wiki/Incipient_wetness_impregnation
105.F. Bonet, V. Delmas, S. Grugeon, R.H. Urbina, P.Y. Silvert, K.T. Elgsissen. Nano Structured Materials 11 (1999) 1277.
106.L. K. Kurihara, G. M. Chow, P. E. Schoen. Nanostructured materials 5 (1995) 607.
107.W. Cai, J. Wan. J.colloid and interface science 305 (2007) 366.
108.S. L. Knupp, W. Li, O. Paschos, T. M. Murray, J. Snyder, P. Haldar. Carbon 46 (2008) 1276.
109.N. Toshima, Y. Wang. Langmuir 10(12) (1994) 4574.
110.X. Li, W. X. Chen, J. Zhao, W. Xing, Z. D. Xu. Carbon 43 (2005) 2168.
111.W. Yu, W. Tu, H. Liu. Langmuir 15 (1999) 6.
112.C. Bock, C. Paquet, M. Couillard, G. A. Botton, B. R. MacDougall. J. Am. Chem. Soc. 126 (2004) 8028.
113.Y.C. Yang, C.H. Wang, Y.K. Hwu, J.H. Je. Materials Chemistry and Physics 100 (2006) 72.
114.C.H. Wang, T.E. Hua, C.C. Chien. Materials Chemistry and Physics 106 (2007) 323.
115.C.H. Wang, C.J.N. Liu, C.L. Wang, T.-E. Hua, J.M. Obliosca, K.H. Lee, Y. Hwu, C.-S. Yang, R.S. Liu, H.M. Lin, J.H. Je, G. Margaritondo. Journal of Physics D: Applied Physics 41 (2008) 195301.
116.B. G. Ershov, A.V. Gordeev. Radiation Physics and Chemistry 77 (2008) 928.
117.M. Kumar, L. Varshney, S. Francis. Radiation Physics and Chemistry 73 (2005) 21.
118.H.B. Bae, S.H. Oh, J.C. Woo, S.H. Choi. J. Nanosci. Nanotechnol. 10 (2010) 6901.
119.J. Belloni, M. Mostafavi, H. Remita, J. L. Marignier, M.O. Delcourt. New J. Chem. 90 (1998) 1239.
120.F. K. Liu, Y. C. Hsu, M. H. Tsai, T.C. Chu. Radiat. Phys. Chem. 67 (2003) 517.
121.T. Lia, H. G. Parka, S. H. Choib. Mater. Chem. Phys. 105 (2007) 325.