本篇論文探討鉑金觸媒催化二氧化碳重組甲烷反應的行為。由於二氧化碳重組法有較高的一氧化碳選擇率，提供較合宜的CO/H2 比例，因此我們便利用CO2與CH4 來進行重組反應產生合成氣。選擇反應性佳的鉑觸媒，以含浸方式製備Pt-Au/Al2O3 合金觸媒，探討觸媒在催化反應中其性質的差異。分別針對不同鉑、金濃度的雙金屬觸媒對於甲烷、二氧化碳及重組反應活性的測試。利用程溫甲烷裂解反應、甲烷分解反應後之程溫氧化脫附鑑定、甲烷分解反應後之程溫二氧化碳反應鑑定、合成氣反應後程溫氧化脫附鑑定與X 光繞射光譜(XRD)等實驗，分析甲烷分解反應與合成氣反應在鉑金觸媒上產生的積碳形式、反應性與表面特性。由實驗可知鉑金觸媒的反應活性比純鉑觸媒好，且鉑金觸媒與純鉑觸媒的所產生的積碳型式並不相同，意謂著甲烷分解的反應機制也不相同。同時也可知觸媒經過合成氣反應後再經二氧化碳處理所產生積碳與合成氣反應所產生的積碳對氫氣的反應性也不一樣。

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誌謝 .................................................................................................................................. i
摘要 ..................................................................................................................................ii
目錄 ................................................................................................................................. iii
圖目錄 .............................................................................................................................. vi
表目錄 ............................................................................................................................ viii
壹、緒論 .......................................................................................................................... 1
§ 1-1 前言 ................................................................................................................ 1
貳、文獻回顧 .................................................................................................................. 3
§ 2-1 二氧化碳重組甲烷反應 ................................................................................ 3
§ 2-2 二氧化碳重組甲烷反應相關化學反應式 .................................................... 4
§ 2-3 二氧化碳重組甲烷反應機制 ........................................................................ 5
§ 2-4 甲烷活化 ........................................................................................................ 8
§ 2-5 二氧化碳的活化 .......................................................................................... 10
§ 2-6 觸媒的失活 .................................................................................................. 11
§ 2-6-1 Ru、Rh 觸媒 .................................................................................. 11
§ 2-6-2 Ni 觸媒........................................................................................... 13
§ 2-6-3 Pt 觸媒 ........................................................................................... 14
§ 2-7 積碳 .............................................................................................................. 15
参、實驗裝置與方法 .................................................................................................... 19
§ 3-1 實驗藥品 ...................................................................................................... 19
§ 3-2 反應氣體 ...................................................................................................... 19
§ 3-3 實驗裝置 ...................................................................................................... 20
§ 3-3-1 反應爐............................................................................................... 20
iv
§ 3-3-2 反應爐－GC ..................................................................................... 21
§ 3-3-3 反應爐－MS ..................................................................................... 22
§ 3-3-4 反應爐－TCD................................................................................... 23
§ 3-3-5 XRD ................................................................................................ 24
§ 3-4 觸媒配製 .................................................................................................... 25
§ 3-5 實驗方法 .................................................................................................... 26
§ 3-5-1 氧化態鉑金觸媒合成氣反應活性測定......................................... 26
§ 3-5-2 還原態鉑金觸媒程溫甲烷裂解反應............................................. 26
§ 3-5-3 還原態鉑金觸媒甲烷分解反應後之程溫氧化脫附鑑定............. 27
§ 3-5-4 還原態鉑金觸媒甲烷分解反應後之程溫二氧化碳反應之鑑定. 28
§ 3-5-5 氧化態鉑金觸媒合成氣反應後之程溫氧化脫附鑑定................. 29
§ 3-5-6 氧化態鉑金觸媒合成氣反應後接二氧化碳反應之程溫氧化脫附
鑑定 ................................................................................................................ 29
§ 3-5-7 氧化態鉑金觸媒合成氣反應後接氫氣反應之程溫氧化脫附鑑定
........................................................................................................................ 30
§ 3-5-8 氧化態鉑金觸媒合成氣反應後接二氧化碳反應再接氫氣反應之
程溫氧化脫附鑑定 ........................................................................................ 30
§ 3-5-9 還原態鉑金觸媒合成氣反應活性測定......................................... 31
肆、結果與討論 ............................................................................................................ 32
§ 4-1 氧化態鉑金觸媒合成氣反應活性測定 .................................................... 32
§ 4-2 還原態鉑金觸媒程溫甲烷裂解反應 ........................................................ 35
§ 4-3 還原態鉑金觸媒甲烷分解反應後之程溫氧化脫附鑑定 ........................ 37
§ 4-4 還原態鉑金觸媒甲烷分解反應後之程溫二氧化碳反應之鑑定 ............ 46
§ 4-5 氧化態鉑金觸媒合成氣反應後之程溫氧化脫附鑑定 ............................ 53
§ 4-6 氧化態鉑金觸媒合成氣反應後接二氧化碳反應之程溫氧化脫附鑑定 55
v
§ 4-7 氧化態鉑金觸媒合成氣反應－二氧化碳與氫氣反應之程溫氧化脫附鑑
定 ............................................................................................................................ 55
§ 4-8 還原態鉑金觸媒合成氣反應活性測定 .................................................... 58
伍、結論 ........................................................................................................................ 59
陸、参考文獻 ................................................................................................................ 60

【1】J. R. Rostrup-Niesen and J. H. B. Hansen, J. Catal. 144, 38 (1993).
【2】A. P. Farkas and F. Solymosi, J. Phys. Chem. C. 113, 19930 (2009).
【3】A. P. Farkas and F. Solymosi, J. Phys. Chem. C. 114, 16979 (2010).
【4】A. M. Efstathiou, A. Kladi, V. A. Tsipouriari, and X. E. Verykios,
J. Catal. 158, 64 (1996).
【5】J. Erdohelyi, Cserenyi, and F. Solymosi, J. Catal. 141, 287 (1993).
【6】V. C. H. Kroll, H.M. Swaan, S. Lacombe, and C. Mirodatos,
J. Catal. 104, 387 (1996).
【7】C. T. Au, and H. Y. Wang, Appl. Catal. A. 155, 239 (1997).
【8】S. T. Ceyer, Q. Y. Yang, M. B. Lee, J. D. Beckerle, and A. D. Johnson,
Methane Conversion Elservier Amsterdam. 51 (1998).
【9】A. C. Luntz and J. Harries, Surf. Sci. 258, 397 (1991).
【10】T. P. Beebe, D. W. Goodman, B. D. Kay, and J. T. Yates ,
J. Phys. Chem. 87, 2305 (1987).
【11】F. Solymosi, J. Mol. Cata. 65, 337 (1991).
【12】N. Matsui, K. Anzai, N. Akamatsu, K. Nakagawa, N. Ikenaga, and
T. Suzuki, Appl. Catal. A. 179, 247 (1999).
【13】Z. L. Zhang, V. A. Tsipouriari, A. M. Efstathiou, and X. E. Verykios,
J. Catal. 158, 51 (1996).
【14】J. Nakumara, K. Aikawa, K. Sato, and T. Uchijima, Catal. Lett. 25, 265 (1994).
【15】S. Wang and G. Q. Lu, Appl. Catal. A. 169, 271 (1998).
【16】R. Molina and G. Poncelet, J. Phys. Chem. B. 103, 11290 (1999).
【17】S. S. Wang and G. Q. Lu, Appl. Catal. B. 16, 269 (1998).
61
【18】M. C. J. Bradford and M. A. Vannice, Appl. Catal. A. 142, 73 (1996).
【19】E. Ruckenstein and Y. H. Hu, Appl. Catal. 133, 149 (1995).
【20】Y. G. Chen, K. Tomishige, and K. Yokoyama, J. Catal. 184, 479 (1999).
【21】A. E. Quincoces, S. Dicundo, and A. M. Alvarez, Material Lett. 50, 21 (2001).
【22】Toshihiko, Osaki, Toshiaki, and Mori, J. Catal. 204, 89 (2001).
【23】J. H. Bitter, W. Hally, L. Seshan, J. G. Van-Ommen, and J. A.Leachr,
Catal. Today. 29, 349 (1996).
【24】K. Nagaoka, K. Seshan, Ken-ichi Aika, and J. A. Lercher,
J. Catal. 197, 34 (2001).
【25】F. Solymosi, G. Kutsan, and A. Erdohelyi, Catal. Lett. 11, 149 (1991).
【26】A. Sacco, F. W. A. H. Geurts, and G. A. Jablonski, J. Catal. 161, 409 (1989).
【27】V. C. H. Kroll, H. M. Swaan, and C. Mirodatos, J. Catal. 161, 409 (1996).
【28】M. Ito, T. Tagawa, and S. Goto, Appl. Catal. A. 177, 15 (1999).
【29】A. J. H. Kock, P.K. De Bokx, E. Boellaard, W. Klop, and J. W. Geus,
J. Catal. 96, 468 (1985).
【30】K. Tomishige, O. Yamazaki, Y.G. Chen, K. Yokoyama, X.H. Li, and
K. Fujimoto, Catal. Today. 45, 35 (1998).
【31】H. M. Swaan, V. C. H. Kroll, G. A. Martin, and C. Mirodatos,
Catal. Today. 21, 571 (1994).
【32】J. J. Gamman, G. J. Millar, G. Rose, and J. Drennan,
J. Chem. Soc. Faraday Trans. 94(5), 701 (1998).
【33】Z. L. Zhang and X.E. Verykios, Catal. Today. 21, 589 (1994).
【34】S. Wang and G.Q. Lu, Energy Fuels. 10, 896 (1996).
【35】M. T. Tavares, I. Alstrup, C. A. Bernardo, and J. R. Rpstrup-Nielsen,
J. Catal. 147, 525 (1994).
62
【36】C. H. Bartholomew, Catal. Rev.Sci. Eng. 24(1), 67 (1982).
【37】曾立德, 銅鎳組成觸媒與表面碳物種反應行為, (2003).
【38】B. D. Chandler, C. G. Long, J. D. Gilbertson, C. J. Pursell, G. Vijayaraghavan,
and K. J. Stevenson, J. Phys. Chem. C. 114, 11498 (2010).