臺灣博碩士論文加值系統

本研究以膠體先驅物法開發低溫燃料電池用的碳黑負載的鉑(Pt)與鉑釕(PtRu)合金陽極觸媒，並以循環伏安法及旋轉電極探討Pt/C與PtRu/C觸媒電極上一氧化碳的吸附和其吸附對氫氣氧化反應的影響。使用原料為PtCl2、RuCl3與N(oct4)[Bet3H]，製備所得的5.4~27.2wt% Pt/C與6.5~26.6wt% PtRu/C觸媒之Pt和PtRu粒徑，以X-ray繞射分析儀和穿透式顯微鏡量測，範圍分別為3.1~8.9 nm與2.6~3.3 nm，其值比商用Pt/C與PtRu/C觸媒中的略大。本研究藉由一氧化碳吸附降低觸媒活性面積，利用旋轉電極方法求得Pt/C與PtRu/C觸媒層氫氣氧化的電流密度，並進而測得交換電流密度。在 28℃下於0.5M H2SO4中測得之Pt/C和PtRu/C的交換電流密度分別為5mAcm-2 和1.4mAcm-2。Pt/C對氫氣氧化的電催化活性比PtRu/C好，但前者吸附一氧化碳的速率比後者快。
本研究的結果有助於開發抗一氧化碳毒化的含鉑合金，應用為低溫燃料電池的陽極觸媒材料。

Platinum and platinum-ruthenium alloy catalysts on carbon were prepared by colloidal precursor technique. The adsorption of CO and its effect on the hydrogen oxidation reaction on the catalyst were investigated by cyclic voltammetry (CV) and the rotating disk electrode (RDE) techniques. PtCl2, RuCl3 and N(oct4)[ Bet3H] were used to prepared the catalysts. The particle sizes of Pt and PtRu for 5.4~27.2 wt% Pt/C and 6.5~26.6 wt% PtRu/C prepared, determined by X-ray diffraction and transmission electron microscope, were in the range of 3.1~8.9 nm and 2.6~3.3 nm, respectively, which are slightly larger than those of commercial catalysts.
By reducing the electro-active surface area of the catalyst through the adsorption of CO, the current density in the catalyst layer and thus the exchange current density for hydrogen oxidation reaction on the catalyst can be measured using the rotating disk electrode (RDE) method. The exchange current densities of Pt/C and PtRu/C in 0.5M H2SO4 at 28℃ were determined to be 5mAcm-2 and 1.4mAcm-2, respectively. Pt/C had higher electrocatalytic activity for hydrogen oxidation than PtRu/C, but Pt/C was poisioned by CO faster than PtRu/C.
The results of this research may contribute to the development of CO-tolerant platinum-based alloy anode catalysts for low-temperature fuel cells.

中文摘要 vi
Abstract vii
符號說明 viii
圖表索引 x
第一章 緒論 1
1-1 研究背景 1
1-2 研究目標 3
第二章 文獻回顧 4
2-1 燃料電池發展 4
2-1-1發展歷史 4
2-1-2 燃料電池的效益 6
2-1-3 燃料電池種類 7
2-2 質子交換膜燃料電池 7
2-2-1 電催化觸媒及其製備 10
2-2-2 質子交換膜 12
2-2-3 氣體擴散電極 15
2-2-4 電極反應 16
2-2-5 燃料供應 20
2-3 電化學表面積的測量 22
2-4 氫氣氧化動力學與一氧化碳的毒化 23
第三章 實驗與分析方法 29
3-1 試料來源 29
3-2 Pt/C與PtRu/C觸媒製備方法 30
3-2-1 碳黑前處理 31
3-2-2 電催化觸媒製備 31
3-2-3電極製備 33
3-3 電化學實驗 35
3-3-1 電化學分析儀器 35
3-3-2 電化學活性表面積測量 35
3-3-3 氫氣氧化反應 37
3-3-4 一氧化碳吸附 38
3-4 物性分析方法與儀器 41
3-4-1 熱重分析與熱差分析儀（TG-DTA） 41
3-4-2 X-ray繞射分析（XRD） 41
3-4-3 穿透式電子顯微鏡分析（TEM） 42
3-5 動力學分析 42
3-5-1 氫氣氧化動力分析 42
3-5-2 CO/H2下的氫氣氧化反應動力學分析 45
第四章 結果與討論 48
4-1 Pt/C觸媒結構性質與電化學分析 48
4-1-1 觸媒含量分析 48
4-1-2 粒徑與晶相探討 51
4-1-3 電極電化學活性表面積量測 60
4-1-4 一氧化碳毒化現象 62
4-1-5 氫氣氧化反應 66
4-2 PtRu/C觸媒結構性質與電化學分析 83
4-2-1 觸媒含量分析 83
4-2-2 粒徑與晶相探討 85
4-2-3 電極電化學活性表面積量測 94
4-2-4 一氧化碳毒化現象 96
4-2-5 氫氣氧化反應 100
4-3 Pt/C與PtRu/C觸媒特性與電化學分析比較 116
4-3-1 粒徑與電化學活性面積比較 116
4-3-2 一氧化碳毒化現象比較 118
第五章 結論 124
參考文獻 125

Aberdam, D.; Durand, R.; Faure, R.; Gloagren, F.; Hazemann, J. L.; Herrero, E.; Kabbabi, A.; Ulrich, O., “X-ray absorption near edge structure study of the electro-oxidation reaction of CO on Pt50Ru50 nanoparticles” Journal of Electroanalytical Chemistry, 398, 43-47 (1995)

Almeida, S. H. and Kawano. Y., “Effects of X-ray radiation on Nafion membrane” Polymer Degradation and Stability, 62, 291-297 (1998)

Antolini, E., L. Giorgi, A. Pozio, and E. Passalacqua, “Influence of Nafion Loading in the Catalyst Layer of Gas-Diffusion Electrodes for PEFC”, J. Power Sources, 77, 136-142 (1999)

Arenz, M.; Stamenkovic, B.; Blizanzc, B. B.; Mayrhofer, K. J.; Markovic, K. V.; Ross, P. N., “Carbon-supported Pt-Sn electrocatalysts for the anodic oxidation of H2, CO, and H2/CO mixtures. Part II: The structure-activity relationship” J. Catal., 232, 402-410 (2005)

Bard, A. J. and Faulkner, L. R., “Electrochemical Method-Fundanmentals and Applications” Wiley, New Youk, U.S.A.(2001)

Bird, R. B.; Stewart, W. E.; Lightfoot, E. W.,”Transport Phenomena” John Wiley and Sons, Inc., New Youk, U.S.A. (2002)

Bonnemann, H.; Brijoux, W.; Brinkmann, R.; Fretzen, R.; Joussen, T.; Koppler, R.; Korall, B.; Neiteler, P.; Richter, J., ” Preparation, characterization, and application of fine metal particles and metal colloids using hydrotriorganoborates” J. Mol. Catal., 86, 129-177 (1994)

Bonnemann, H.; Braun, G.; Brijoux, W.; Brinkmann, R.; Tilling, A. S.; Seevogel, K.; Siepen, K., ” Nanoscale colloidal metals and alloys stabilized by solvents and surfactants - Preparation and use as catalyst precursors” J. Orgamometal. Chem., 520, 143-162 (1996)

Brankovic, S. R.; Marinkovic, N. S.; Wang, J. X.; Adzic, R. R., “Carbon monoxide oxidation on bare and Pt-modified Ru(1010) and Ru(0001) single crystal electrodes” J. Electrochem.Chem., 532, 57-66 (2002)

Breiter, M. W., “Reaction mechanisms of the H2 oxidation/evolution reaction” Handbook of Fuel Cells, Chap.25, 261-267 (2003)

Carmo, M.; Santos, A. R.; Poco, J. G. R.; Linardi, M.,” Physical and electrochemical evaluation of commercial carbon black as electrocatalysts supports for DMFC applications” Journal of Power Sources, 173, 860-866 (2007)

Carrette, L.; Friendrich, K. A.; Stimming, U., “Fuel Cells – Fundamental and Applications”, Fuel Cells, 1, 162-193 (2001)

Ciureanu, M. and H. Wang, “Electrochemical Impedance Study of Electrode Membrane Assemblies in PEM Fuel Cells I. Electro-oxidation of H2 and H2/CO Mixtures on Pt-Based Gas-Diffusion Electrodes”, J. Electrochem. Soc., 146, 4031 (1999).

Deivaraj, T. C. and Lee, J. Y., “Preparation of carbon-supported PtRu nanoparticles for direct methanol fuel cell applications- a comparative study” J. Power Sources., 142, 43-49 (2005)

Elezovic, N. R.; Gajic-Krstajic, Lj.; Radmilovic, V.; Vracar, Lj.; Krstajic, N. V.; “Effect of chemisorbed carbon monoxide on Pt/C electrode on the mechanism of the hydrogen oxidation reaction” Electrochimica Acta, 54, 1375-1382 (2008)

Fournier, J.; Faubert, G.; Tilquin, J. Y.; Cote, R.; Guay, D.; Dodelet, J. P. ” High-performance, low Pt content catalysts for the electroreduction of oxygen in polymer-electrolyte fuel cells” J. Electrochem. Soc., 144, 145-154 (1997)

Gasteiger, H. A.; Markovic, N.; Ross, P. N., “H2 and CO Electrooxidation on Well-Characterized Pt, Ru, and Pt-Ru. 2. Rotating Disk Electrode Studies of CO/H2 Mixtures at 62 .degree.C” J. Phys. Chem., 99, 16757-16767 (1995)

Gao, J. W.; Zhao, T. S.; Prabhuram, J.; Chen, R.; Wong, C. W., “Preparation and characterization of a PtRu/C nanocatalyst for direct methanol fuel cells” Electrochim. Acta, 51, 754-763 (2005)

Gojkovic, S. L.; Vidakovic, T. R.; Durovic, D. R., “Kinetic study of methanol oxidation on carbon-supported PtRu electrocatalyst” Electrochim. Acta, 48, 3607-3614 (2003)

Gottesfeld, S. and Pafford, J., “A New Approach to the Problem of Carbon Monoxide Poisoning in Fuel Cells Operating at Low Temperatures” J. Electrochem. Soc., 135, 2651-2652 (1988)

Gotz, M. and Wendt, H., ”Binary and ternary anode catalyst formulations including the elements W, Sn and Mo for PEMFCs operated on methanol or reformate gas” Electrochim. Acta, 43, 3637-3644 (1998)

Hamnett, A., “Mechanism and electrocatalysis in the direct methanol fuel cell”, Catalysis Today, 38, 445-457 (1997)

Haug, A. T., R. E. White, J. W. Weidner, W. Huang, S. Shi, N. Rana, S. Grunow, T. C. Stoner, and A. E. Kaloyeros, “Using Sputter Deposition to Increase CO Tolerance in a Proton-Exchange Membrane Fuel Cell”, J. Electrochem. Soc., 149, A868-A872 (2002)

Heal, G. R. and Mkayula, L. L., ”The preparation of palladium metal catalysts supported on carbon part I: Selection and treatment of the carbons” Carbon, 26, 815-823 (1988)

Higuchi E.; Uchida H.; Watanabe M., “Effect of loading level in platinum-dispersed carbon black electrocatalysts on oxygen reduction activity evaluated by rotating disk electrode” Journal of Electroanalytical Chemistry, 583, 69-76 (2005)

Hoogsteen, W. and Fokkink, L. G. J., ” Polymer-Stabilized Pd Sols: Kinetics of Sol Formation and Stabilization Mechanism” J. Colloid Interface Sci., 175, 12-26 (1995)
Kinoshita, K., Electrochemical Oxygen Technology, John Wiley & Sons, New York, U.S.A. (1992)

Kordesch, K. V. and Simader, G. R., “Environmental-impact of fuel-cell technology”, Chem Rev., 95, 191-207 (1996).

Lin, R. B. and Shih, S. M., “Kinetic analysis of the hydrogen oxidation reaction at Nafion film covered Pt-black rotating disk electrodes”, Jorunal of the Chinese Institute of Chemical Engineers, 39, 475-481 (2008)

Liu, W. J., B. L. Wu, and C. S. Cha, “Surface diffusion and the spillover of H-adatoms and oxygen-containing surface species on the surface of carbon black and Pt/C porous electrodes”, J. Electroanal. Chem., 476, 101-108 (1999)

Lizcano-Valbuena, W. H.; Paganin, V. A.; Gonzalez, E. R., “Methanol electro-oxidation on gas diffusion electrodes prepared with Pt-Ru/C catalysts” Electrochimica Acta., 47, 3715-3722 (2002)

Lizcano-Valbuena, W. H.; Paganin, V. A.; Carlos, A. P.; Leite, F.; Galembeck, E. R.; “Catalysts for DMFC: relation between morphology and electrochemical performance” Electrochimica Acta., 48, 3869-3878 (2003)

Lizcano-Valbuena, W. H.; de Azevedo, D. C.; Gonzalez, E. R., “Supported metal nanoparticles as electrocatalysts for low-temperature fuel cells” Electrochimica Acta.,49, 1289-1395 (2004)

Lu, C.; Rice, C.; Masel, R. I.; Babu, P. L.; Waszczuk, P.; Kim, H. S.; Oldfoeld, E.; Wieckowaki, A., “UHV, Electrochemical NMR, and Electrochemical Studies of Platinum/Ruthenium Fuel Cell Catalysts” J. Phys. Chem. B., 106, 9581-9589 (2002)

Luo, J.; Maye, M. M.; Kariuki, N. N.; Wang, L.; Njoki, P.; Lin, Y.; Schadt, M.; Naslund, H. R.; Zhong, C.J., “Electrocatalytic oxidation of methanol: carbon-supported gold-platunum nanoparticle catalysts prepared by two-phase protocol” Catalysis Today., 99, 291-297 (2005)

Maruyama, J., M. Inaba, K. Katakura, Z. Ogumi, and Z. Takehara, “Influence of Nafion film on the kinetics of anodic hydrogen oxidation“, J. Electroanal. Chem., 447, 201-209 (1998)

McBreen, J., “Voltammetric Studies of Electrodes in Contact with ionomeric Membranes”, J. Electrochem. Soc., 132, 1112-1115 (1985)

Metha, V., and J. S. Cooper, “Review and analysis of PEM fuel cell design and manufacturing”, J. Power Sources, 114, 32-53 (2003)

Mello, R. M. Q. and E. A. Ticianelli, “Kinetic study of the hydrogen oxidation reaction on platinum and Nafion covered platinum electrodes”, Electrochim. Acta., 42, 1031-1039 (1997)

Mukerjee, S.; Urian, R. C.; Lee, S. J.; Ticianelli, J.; McBreen, J., “Electrocatalysis of CO tolerance by carbon-supported PtMo electrocatalysts in PEMFCs” J. Electrochem. Soc., 151, A1094-A1103 (2004)

Okada, T., J. Dale, Y. Ayato, O. A. Asbjornsen, M. Yuasa, and I. Sekine, “Unprecedented Effects of Impurity Cations on the Oxygen Reduction Kinetics at Platinum Electrodes Covered with Perfluorinated Ionomer”, Langmuir, 15, 8490-8496 (1999)

Okada, T., Y. Ayato, J. Dale, M. Yuasa, I. Sekine, and O. A. Asbjornsen, “Oxygen reduction kinetics at platinum electrode covered with perfluorinated ionomer in the presence of impurity cations Fe3+, Ni2+ and Cu2+”, Phys. Chem. Chem. Phys., 2, 3255-3261 (2000)

Okada, T., Y. Ayato, H. Satou, M. Yuasa, and I. Sekine, “The Effects of Impurity Cations on the Oxygen Reduction Kinetics at Platinum Electrodes Covered with Perfluorinated Ionomer”, J. Phys. Chem. B., 105, 6980-6986 (2001)

Okada, T., “Effects of ionic contaminants”, In: Vielstich, W., H. A. Gasteiger, and A. Lamm (ed), Handbook of Fuel Cells — Fundamentals, Technology and Applications, John Wiley & Sons, 3, pp.627-646 (2003)

Parsons, R. and VanderNoot, T., “The oxidation of small organic molecules : A survey of recent fuel cell related research” J. Electroanal. Chem., 257, 9-45 (1988)

Passalacqua, E., F. Lufrano, G. Squadrito, A. Patti, and L. Giorgi, “Nafion content in the catalyst layer of polymer electrolyte fuel cells: effects on structure and performance”, Electrochim. Acta., 46, 799-805 (2001)

Paulus, U. A.; Endruschat, U.; Feldmeyer, G. J.; Schmidt, T. J.; Bonnemann, H.; Behm, R. J., ” New PtRu alloy colloids as precursors for fuel cell catalysts” J. Catalysis, 195, 383-393 (2000)

Paulus, U. A.; Schmidt, T. J.; Gasteiger, H. A.; Behm, R. J., ” Oxygen reduction on a high-surface area Pt/Vulcan carbon catalyst: a thin-film rotating ring-disk electrode study” J. Electroanal. Chem., 495, 134-145 (2001)

Paulus, U. A., Z. Veziridis, B. Schnyder, M. Kuhnke, G. G. Scherer, and A. Wokaun, “Fundamental investigation of catalyst utilization at the electrode/solid polymer electrolyte interface Part I. Development of a model system”, J. Electroanal. Chem., 541, 77-91 (2003)

Perez, J., E. R. Gonzalez, and E. A. Ticianelli, “Oxygen electrocatalysis on thin porous coating rotating platinum electrodes”, Electrochim. Acta., 44, 1329-1339 (1998).

Pozio, A., M. D. Francesco, A. Cemmi, F. Cardellini, and L. Giorgi, “Comparison of high surface Pt/C catalysts by cyclic voltammetry”, J. Power Sources, 105, 13-19 (2002)

Roen, L. M., C. H. Paik, and T. D. Jarvi, “Electrocatalytic Corrosion of Carbon Support in PEMFC Cathodes”, Electrochem. Solid-State Lett., 7, A19-A22 (2004)
Rauhe, B. R.; McLarnon, F. R.; Cairns, E. J., “Direct anodic oxidation of methanol on supported platinum/ruthenium catalyst in aqueous cesium carbonate” J. Electrochem. Soc., 142, 1073-1084 (1995)

Roy, S. C.; Christensen, P. A.; Hamnett, A.; Thomas, K. M.; Trapp, V., “Direct methanol fuel cell cathodes with sulfur and nitrogen-based carbon functionality” J. Electrochem. Soc., 143, 3073-3079 (1996)

Sarma, L. S.; Lin, T. D.; Tsai, Y. W.; Chen, J. M.; Hwang, B. J., “Carbon-supported Pt-Ru catalysts prepared by the Nafion stabilized alcohol-reduction method for application in direct methanol fuel cells” J. Power Sources., 139, 44-54 (2005)

Sasikumar, G., J. W. Ihm, and H. Ryu, “Optimum Nafion content in PEM fuel cell electrodes“, Electrochim. Acta., 50, 601-605 (2004)

Schmidt, T. J.; Noeske, M.; Gasteiger, H. A.; Behm, R. J., ” Electrocatalytic activity of PtRu alloy colloids for CO and CO/H-2 electrooxidation: Stripping voltammetry and rotating disk measurements” Langmuir, 13, 2591-2595 (1997)

Schmidt, T. J.; Gasteiger, H. A.; Stab G. D.; Urban, P. M.; Kolb, D. M.; Behm, R. J.’ “ Characterization of high-surface-area electrocatalysts using a rotating disk electrode configuration” J. Electrochm. Soc., 145, 2354-2358 (1998) (a)

Schmidt, T. J.; Noeske, M.; Gosteiger H. A.; Behm, R. J., “PtRu alloy colloids as precursors for fuel cell catalysts - A combined XPS, AFM, HRTEM, and RDE study” J. Electrochm. Soc., 145, 925-931 (1998) (b)

Schmidt, T. J. and H. A. Gasteiger, and A. Lamm (ed), Handbook of Fuel Cells — Fundamentals, Technology and Applications, vol. 2, John Wiley & Sons, pp.316-333 (2003)

Shan, J. and Pickup, P. G., ”Characterization of polymer supported catalysts by cyclic voltammetry and rotating disk voltammetry” Electrochem. Acta., 46, 119-125 (2000)
Smith, J. M.; VanNess, H. C.; Abbott, M. M., “ Introduction to chemical engineering thermodynamics“ 5th , 1996

Ticianelli. E. A.; Beery, J. G.; Srinivasan, S., “Dependence of performance of solid polymer electrolyte fuel cells with low platinum loading on morphologic characteristics of the electrodes” J. Appl. Electrochem., 21, 597 (1991)

Tamizhmani, G., J. P. Dodelet, and D. Guay, “Crystallite Size Effects of Carbon-Supported Platinum on Oxygen Reduction in Liquid Acids”, J. Electrochem. Soc., 143, 18-23 (1996)

Toshima, N. and Yonezawa, T., “Bimetallic nanoparticles - novel materials for chemical and physical applications” New J. Chem., 22, 1179-1201 (1998)

Toshima, N.; Shiraishi, Y.; Teranishi,T.; Miyake, M.; Tominage, T, Watanabe, H.; Brijoux, W.; Bonnemann, H.; Schmid, G., ” Various ligand-stabilized metal nanoclusters as homogeneous and heterogeneous catalysts in the liquid phase” Appl. Organometal. Chem., 15, 178-196 (2001)

Uchida, M.; Aoyama, Y.; Tanabe, M.; Yanagihara, N., Eda, N.; Ohta, A., “Influences of Both Carbon Supports and Heat-Treatment of Supported Catalyst on Electrochemical Oxidation of Methanol” J. Electrochem. Soc., 142, 2572-2576 (1995)

Vielstich, W., H. A. Gasteiger, and A. Lamm (ed), “Handbook of Fuel Cells — Fundamentals Technology and Applications”, John Wiley & Sons, (2003)

Vogel, W.; Lundquist, J.; Ross, P.; Stonehart, P. “Reaction pathways and poisons-Π the rate controlling step for electrochemical oxidation of hydrogen on Pt in acid and poisoning of the reaction by CO“ Electrochimica Acta., 20, 79-93 (1975)

Vogel, W.; Britz, P.; Bonnemann, H.; Rothe, J.; Hormes, J.; “Structure and chemical composition of surfactant-stabilized PtRu alloy colloids” J. Phys. Chem. B, 101, 11029-11036 (1997)
Wang J.G., Neoh, K. G., and Kang, E.T., “Preparation of Nanosized Metallic Particles in Polyaniline “ J. Colloid Interface Sci. , 239, 78-86 (2001).

Wright, P. V., “Polymer electrolytes—the early days”, Electrochim. Acta., 43, 1137-1143 (1998)

Wasmus, S. and Kuver, A., “Methanol oxidation and direct methanol fuel cells: a selective review” J. Electroanal. Chem., 461, 14-31 (1999)

Watanabe, M.; Igarashi H.; Yosioka, K., “An experimental prediction of the preparation condition of nafion-coated catalyst layers for PEFCs” Electrochimica Acta., 40, 329-334 (1995)

Watanabe, M.; Uchida, H.; Seki, Y.; Emori, M.; Stonehart, P., “Self-humidifying polymer electrolyte membranes for fuel cells” J. Electrochem. Soc., 143, 3847-2852 (1996)

Ye, S.; Vijh, A. K.; Dao, L. H., “A New Fuel Cell Electrocatalyst Based on Carbonized Polyacrylonitrile Foam” J. Electrochem. Soc., 144, 90-95 (1997)

Zeng, R., J. Pang, and H. Zhu, “Modification of a Nafion ion exchange membrane by a plasma polymerization process”, J. Electroanal. Chem., 490, 102-106 (2000)

衣寶廉，”燃料電池—原理與應用”，五南 (2005)

林仁斌”氫氣在燃料電池白金觸媒上氧化反應之動力學研究” ，博士論文，國立台灣大學，台北，台灣 (2005)