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研究生：	蘇媛媛 Masrul, Suryaneta-Binti
論文名稱：	應用於直接乙醇燃料電池的PtSnP/C觸媒之研究 Investigation on PtSnP/C Catalyst for Direct Ethanol Fuel Cell
指導教授：	楊明長 Yang, Ming-Chang
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	英文
論文頁數：	103
中文關鍵詞：	乙醇燃料電池、陽極觸媒
外文關鍵詞：	anode catalyst, direct ethanol fuel cell, taguchi method
相關次數：	點閱：83 下載：1
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乙醇燃料電池的陽極氧化反應有許多中間產物及副產物產生，反應機制非常複雜，故陽極觸媒活性為效能增進的關鍵因素。陽極觸媒為將金屬觸媒擔在碳黑，常使用到的金屬觸媒是白金，白金對乙醇氧化具有高活性，卻有中間產物毒化觸媒的問題存在。為了增進金屬觸媒對乙醇氧化的電化學活性，常會將白金與其他金屬製備為二合金或三合金金屬觸媒，其中PtSn/C具有高的乙醇氧化活性。
本研究中，利用NaBH4作為還原劑製備Pt/C、PtSn/C和PtSnRu/C陽極觸媒，與利用次磷酸鈉為還原劑製備PtSnP/C陽極觸媒，以獲取相同pt擔載量。在半電池中，以循環伏安法做測試，PtSnP/C相對於Pt/C與PtSn/C的峰電流分別高25 %與8 %，但較PtSnRu/C 效能降低了4.8 %。但PtSnP/C起始電位較PtSnRu/C負，可由此判斷其有較高的活性，且較低成本。
在pH值為14、迴流溫度90 oC下製備PtSnP/C陽極觸媒，利用水為溶劑控制PtCl6-2濃度，發現高濃度的PtCl6-2溶液可同時增加磷在碳黑上擔載的比例，與降低合金金屬的觸媒粒徑。
在探討PtSnP/C為陽極觸媒活性的實驗中利用循環伏安法及線性掃描做測試，使用田中實驗設計法獲得高活性的陽極觸媒的最佳的實驗條件為：用1350毫克NaH2PO2還原247.5毫克的氯鉑酸與39.5毫克四氯化錫製備金屬觸媒，將其擔載在300毫克的碳黑上，並使用187.5毫克為穩定劑。

For the anode catalyst of direct ethanol fuel cell, the reactivity of Ethanol Oxidation Reaction (EOR) that has multistep mechanism, a number of adsorbed intermediates and byproducts need improvement. Platinum is recognized as the most active metal for ethanol oxidation but still have problems such as inhibition or poisoning by intermediates. In order to improve the electrocatalytic activity of ethanol oxidation, researches for modifying Platinum with second and/or third metal were common and PtSn/C catalyst lead to improvement in the ethanol oxidation.
In this study, Pt/C, PtSn/C, PtSnRu/C catalysts that used NaBH4 as reducing agent and PtSnP/C catalyst that used sodium hypophosphite as reducing agent and source of phosphorus have been prepared with same loading of platinum. The first peak current density at positively scanning in a cyclic voltammogram have shown that activity of PtSnP/C was higher than those of Pt/C and PtSn/C by 25 % and 8 %, but lower than PtSnRu/C by 4.8 %. Although its activity lower than that of PtSnRu/C, but PtSnP/C is less expensive and more active based on more negative onset potential.
Through preparation procedure of PtSnP/C such as pH 14, 90 oC, and 8 hours deposition time, 16 ml water was used as solvent to control the concentration of PtCl62- it was found that higher concentration of PtCl62- gave more amount of phosphorus and smaller size of nanoparticle.
The best PtSnP/C has been studied by finding the optimum loading of each element in catalyst. These experiments used Taguchi method that has been success as reliable, relative low cost, and high quality experiment design. Peak current of cyclic voltammogram and liner sweep potential were used as parameter response. After larger-the-better of signal/noise ratio was applied, the optimum loading of each element are: 247.5 mg of hydrogen hexachloroplatinate (IV) hydrate as platinum precursor, 39.5 mg of tin (IV) chloride pentahydrate as tin precursor, 1350 mg of sodium hypophosphite monohydrate as reducing agent and phosphorus source, 300 mg carbon XC-72 as catalyst support, and 187.5 mg of trisodium citrate dihydrate as stabilizing agent.

LIST OF TABLES ............................................................................................ v
LIST OF FIGURES........................................................................................viii
ACKNOWLEDGMENTS..............................................................................xiv
ABSTRACT IN ENGLISH............................................................................xvi
ABSTRACT IN CHINESE..........................................................................xviii
CHAPTER I INTRODUCTION....................................................................... 1
1.1 BACKGROUND ..................................................................................... 1
1.2 MOTIVATION AND OBJECTIVES...................................................... 3
1.3 OUTLINE OF THE THESIS................................................................... 5
CHAPTER II LITERATURE SURVEY .......................................................... 7
2.1 DIRECT ETHANOL FUEL CELL ..................................................................7
2.1.1 Working Principle of Direct Ethanol Fuel Cell................................. 7
2.1.2 Materials of Catalyst for Direct Ethanol Fuel Cell ........................... 8
2.1.3 Preparation Method of Catalyst for Direct Ethanol Fuel Cell .......... 9
2.1.4 Catalyst Support for Direct Ethanol Fuel Cell ................................ 12
2.1.5 Ethanol Oxidation Reaction ............................................................ 13
2.2 CYCLIC VOLTAMMOGRAM......................................................................19
2.2.1 Fundamental .................................................................................... 19
2.2.2 Data Interpretation........................................................................... 23
CHAPTER III EXPERIMENTAL SECTION................................................ 29
3.1 MATERIALS......................................................................................... 29
3.2 PROCEDURE TO MAKE CATALYSTS ............................................ 30
3.2.1 Preparation Pt/C, PtSn/C, and PtSnRu/C Catalyst for References . 30
3.2.2 Preparation PtSnP/C Catalyst for Study the Effect of Reducing
Agent Variation .............................................................................. 33
3.2.3 Preparation PtSnP/C Catalyst to Study the Effect of pH ................ 39
3.2.4 Preparation PtSnP/C Catalyst to Study the Effect of Phosphorus and
Tin Content ..................................................................................... 39
3.2.5 Preparation PtSnP/C Catalyst for Study the Effect of [PtCl6]2-
Concentration.................................................................................. 39
3.2.6 Preparation PtSnP/C Catalyst for Optimization Catalyst by Taguchi
Method ............................................................................................ 39
3.3 PREPARATION FOR A HALF CELL................................................. 41
3.4 PREPARATION FOR ICP-MS............................................................. 45
CHAPTER IV RESULT AND DISCUSSION............................................... 47
4.1 COMPARISON PtSnP/C CATALYST WITH REFERENCES .......... 47
4.2 EFFECT OF REDUCING AGENT VARIATION ON PtSnP/C
CATALYST PREPARATION PROCEDURE.................................... 55
4.3 EFFECT OF pH VARIATION ON PtSnP/C CATALYST
PREPARATION PROCEDURE.......................................................... 61
4.4 EFFECT OF TIN AND PHOSPHORUS CONTENT IN PtSnP/C
CATALYST.......................................................................................... 63
4.5 EFFECT OF PtCl6
2- CONCENTRATION............................................ 66
4.6 STUDY SOME EFFECTS DURING ELECTROCHEMICAL
MEASUREMENT................................................................................ 74
4.6.1 Effect of Ethanol and Sulfuric Acid Concentration Variation...... 74
4.6.2 Effect of Catalyst Loading Variation ............................................ 77
4.6.3 Effect of Scanning Rate Variation ................................................ 78
4.6.4 Effect of Temperature Variation ................................................... 80
4.6.5 Effect of Forward Scan Limit Variation ....................................... 80
4.7 OPTIMISATION PtSnP/C CATALYST USING TAGUCHI METHOD
............................................................................................................... 81
CHAPTER V CONCLUSION........................................................................ 93
REFERENCES................................................................................................ 95
                                    

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校內：2010-09-04公開
校外：2010-09-04公開

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