36 Reactants in H
2SO
37 Reactants in H
2SO Reactants in H
2SO
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0.0 0.2 0.4 0.6 0.8 1.0
Ru/C
Potential (V vs. SCE)
Current (A)
0.442V
0.05mA PtRu/C 0.495V
0.25mA
Pt/C 0.593V
0.06mA
Fig.18 Pt/C, Pt-Ru/C 及 Ru/C 觸媒電極，在含 CO 電解液中對 CO 轉換 成 CO2的 CV 圖。電解液: 0.5M 硫酸, 掃描範圍: 0~0.9V
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表 3. 脈波與定電流法製備之各種觸媒電極，在硫酸溶液中催化甲醇 和 CO 氧化之半波電位的比較
Half-Wave Potential (V vs. SCE) Preparation
Methods Catalyst/Substrate
COa CH3OHb CH3OH+COc
Pt/C 0.593 0.522 0.638
Pt-Ru/C 0.495 0.517 0.592
Pt/Ti 0.581 0.523 0.653
Pulse
Pt-Ru/Ti 0.500 0.540 0.575
Pt/C 0.560 0.557 0.624
Pt-Ru/C 0.378 0.449 0.510
Pt/Ti 0.545 0.518 0.673
Potentaistat
Pt-Ru/Ti 0.404 0.407 0.478
a CO stripping voltammograms in 0.5M H2SO4
b Cyclic voltammograms in 0.5M H2SO4+0.5M CH3OH
c CO stripping voltammograms in 0.5M H2SO4+0.5M CH3OH
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500 1000 1500 2000 2500 3000 3500 4000
0 20 40 60 80 100
Agi n g rati o ( % )
Time (sec)
Pt/C Pt-Ru/C
圖 19. Pt/C, Pt-Ru/C 及 Ru/C 觸媒電極，在 CO 環境下可由圖中看出 電流密度的衰退情形。電解液: 0.5M H2SO4, 電極電位: 0.5V (vs. SCE)
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四、結論
由實驗結果可得知以下結論：
(一) Ru 在陰極還原從-1.1~-0.4V (vs. SCE)及陽極氧化 0.9~1.1V (vs.
SCE)皆有明顯的 Ru 觸媒沉積。
(二) Pt-Ru 共沉積，陰極還原在-0.2V vs. SCE 電位下，具有較大的沉 積效率及催化活性；陽極氧化則在 0.9V vs. SCE 下可得到較佳之 效果，並顯示陽極沉積會以共沉積效應將溶液中 Pt 和 Ru 附著至 基材表面。
(三) 電解液的配製對 Pt-Ru 共沉積生成電極觸媒的效率和其催化活 性有顯著的影響。RuCl3 和 H2PtCl6 溶液分別配製置放 2 天，生 成穩定的膠體後，再混合作為電解液，有利於陽極沉積；但對陰 極沉積則需二溶液先混合後再置放，電極觸媒具有較大的效率和 催化活性。
(四) 利用脈波沉積法的確能有效沉積高表面積、高催化活性的觸媒 電極，且由實驗可知甲醇在雙金屬觸媒 Pt-Ru/C 電極的氧化半波 電位有往負電位位移的趨勢，亦即在有 Ru 存在時，可促進電極 在甲醇氧化時的催化活性及穩定性，並顯示電化學脈波沉積法能 有效共沉積生成 Pt-Ru 電極觸媒。
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(五) 利用脈波沉積法能有效提高沉積效率，製備高催化活性的觸媒 電極。最適脈波成核電位約為-0.4V vs. SCE。最適成核時間約 3~5 秒。
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五、計畫成果自評
1. 本研究計劃已達成預期之目標，部分研究成果已整理發表於 Electrochimica Acta，其摘要如附件所示。
2. 本實驗後續研究結果目前正補充整理中，準備投稿至相關期刊。
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肆、參考文獻
1. R. Rivera-Norieg, International J. Hydrogen Energy 27 (2002) 457 – 460.
2. Jos´e R.C. Salgado, J. Power Sources 141 (2005) 13–18 3. N. Rajalakshmi, J. Power Sources 140 (2005) 250–257.
4. J. R. C. Salgado, J. Power Sources 138 (2004) 56-60.
5. B. Rajesh, V. Karthik, S. Karthikeyan, K. Ravindranathan Thampi, J.-M. Bonard, B. Viswanathan, Fuel 81 (2002) 2177–2190
6. Zhaolin Liu, Leong Ming Gan, Liang Hong, Weixiang Chen, Jim Yang Lee, Journal of Power Sources 139 (2005) 73–78
7. Ji-Er Huang, Dao-Jun Guo, Ya-Gang Yao, Hu-Lin Li, Journal of Electroanalytical Chemistry 577 (2005) 93–97
8. K.I. Han, J.S. Lee, S.O. Park, S.W. Lee, Y.W. Park, Hasuck Kim, Electrochimica Acta 50 (2004) 791–794
9. T. Matsumoto, T. Komatsu, H. Nakano, K. Arai, Y. Nagashima, E. Yoo, T. Yamazaki, M. Kijima, H. Shimizu, Y. Takasaw, J. Nakamura,
Catalysis Today 90 (2004) 277–281
10. Jose’ Manuel Gatica, Jose’ Marı’a Rodrı’guez-Izquierdo , Daniel Sa’nchez, Concepcio’n Ania , Jose’ Bernardo Parra , Hilario Vidal, Carbon 42 (2004) 3251–3272
11. N. Rajalakshmi, Hojin Ryu, M.M. Shaijumon, S. Ramaprabhu, Journal of Power Sources 140 (2005) 250–257
12. M. Carmo, V.A. Paganin, J.M. Rosolen, E.R. Gonzalez, Journal of Power Sources 142 (2005) 169–176
13. Inˆes Rabelo de Moraes, Welliton Jos´e da Silva, Simone Tronto, Jose Mauricio Rosolen, Journal of Power Sources 160 (2006) 997–1002 14. J. Moreira, I. J. Hydrogen Energy 29 (2004) 915– 920.
15. Hussien Gharibi, J. Power Sources 139 (2005) 61–66.
16. Kyoung Hwan Choi, J. Sourcess 75 (1998)230-235 17. Ruizhi Yang, Carbon 43 (2005) 11-16
18. Hussien Gharibi, J. Power Sources 139 (2005) 61–66.
45
19. L. Dubau, J. Electroanalytical Chemistry 554-555 (2003) 407-41.
20. F. Gloaguen, Electrochimica Acta 44 (1999) 1805-181.
21. Mohamed S. El-Deab , Electrochemistry Communications 7 (2005) 29–34.
22. Zhibin He, Materials Chemistry and Physics 85 (2004) 396–401.
23. Zhibin He, Jinhua Chen , Dengyou Liu, Hao Tang, Wei Deng, Yafei Kuang, Materials Chemistry and Physics 85 (2004) 396–401
24. Zhibin He, Jinhua Chen*, Dengyou Liu, Haihui Zhou, Yafei Kuang, Diamond & Related Materials 13 (2004) 1764– 1770
25. Scott D. Thompson, Larry R. Jordan, Maria Forsyth, Electrochimica Acta 46 (2001) 1657–1663
26. Gang Wu, Yong-Sheng Chen, Bo-Qing Xu, Electrochemistry Communications 7 (2005) 1237–1243
27. Hansung Kim, Nalini P. Subramanian, Branko N. Popov, Journal of Power Sources 138 (2004) 14–24
28. H. Tang, J.H. Che, Z.P. Huang, D.Z. Wang, Z.F. Ren, L.H. Nie, Y.F.
Kuang, S.Z. Yao, Carbon 42 (2004) 191–197
29. Hao Tang, Jinhua Chen, Shouzhuo Yao, Lihua Nie, Yafei Kuang, Zhongping Huang, Dezhi Wang, Zhifeng Ren, Materials Chemistry and
Physics 92 (2005) 548–553
30. Hui-Fang Cui, Jian-Shan Ye, Wei-De Zhang, John Wang, Fwu-Shan Sheu, Journal of Electroanalytical Chemistry 577 (2005) 295–302 31. Gang Wu, Yong-Sheng Chen, Bo-Qing Xu, Electrochemistry
Communications 7 (2005) 1237–1243
32. Minghua Huang, Yan Shen, Wenlong Cheng, Yong Shao, Xuping Sun, Baifeng Liu, Shaojun Dong, , Analytica Chimica Acta 535 (2005) 15–22
33. Mohamed S. El-Deab, Tadashi Sotomura, Takeo Ohsaka, , Electrochemistry Communications 7 (2005) 29–34
34. F. Gloaguen, J.M. Le ger, C. Lamy, A. Marmann, U. Stimming, R.
Vogel, Electrochimica Acta 44 (1999) 1805-1816
35. Zhibin He, Jinhua Chen, Dengyou Liu, Haihui Zhou, Yafei Kuang, Diamond & Related Materials 13 (2004) 1764– 1770
46
36. Z.D. Wei, S.H. Chan, Journal of Electroanalytical Chemistry 569 (2004) 23–33
37. Kyoung Hwan Choi, Ham Sung Kim, Tae Hee Lee, Journal of Power Sourses 78 (1998) 230-235
38. Ge Chen, Zhenyao Wang, Dingguo Xia, Electrochemistry Communications 6 (2004) 268–272
39 Kyoung Hwan Choi, Ham Sung Kim, Tae Hee Lee, Journal of Power Sourses 78 (1998) 230-235
40. F.Vigier, F. Gloaguen, J.M. Leger, C. Lamy, Electrochim. Acta 46 (2001) 4331
41. I. Zhitomirsky, L. Gal-Or, Mater. Lett. 31 (1997) 155 42. I. Zhitomirsky, Mater. Lett. 33 (1998) 305
43. M. Vukovic, D. Cukman, J. Electrochem. 482 (2000) 188
44. K. Kvastek, V. Horvat-Radosevic, J. Electrochem. 511 (2001) 65 45. C.C. Hu, H.R. Chiang, C.C. Wang, J. Solid State Electrochem., Vol.7,
pp477, 2003
46. M. Vukovic, D. Cukman, J. Electroanal. Chem. Vol.474, pp.167, 1999 47. M. Metikos-Hukovic, J. Molecular Catalysis A: Chemical 136 (1998)
78-84