臺灣博碩士論文加值系統

本研究以自製的方式合成Corrole系列過渡金屬環大錯合物為非白金觸媒，取代原有的白金觸媒，並且應用於質子交換膜燃料電池陰極端，比較當中心金屬原子為鈷及鐵時（Co-Corrole, Fe-Corrole）其氧氣還原能力的比較，發現熱處理過後的觸媒具有極佳的還原能力，其中Fe-Corrole相較於Co-Corrole具有更好的還原活性，其電子轉移數可達 3.95和雙氧水產生率約2.5％，而在電池最大輸出功率的部分可達到 330 mW/cm2，可見此觸媒的優勢。在X光吸收光譜分析上，發現Co-Corrole在高溫熱處理後其價數由3+價轉變為2+價，而2+價的鈷在進行氧氣還原反應時，所需要的活化能比起3+的鈷要來得小，所以2+價的鈷會比較容易進行氧氣還原反應；接著進一步以原位X光吸收光譜分析（In-situ XAS）Fe-Corrole觸媒，在反應過程中，可發現在不同電位下，其Fe-N鍵長會隨之改變，再搭配方波伏安法的結果，可以建立Fe-corrole觸媒於氧氣還原反應中的機制。
另一部分是以維他命B9做為新的氮來源前驅物，加以混合過渡金屬和碳載體，經過燒結而形成用於氧氣還原反應之新觸媒(Fe-FA/C)，進而應用於質子交換模燃料電池中。在電化學測試中其觸媒表現出絕佳的活性，傾向於理想四個電子轉移之反應。而在電池總輸出功率的部分可達到 330 mW/cm2，以及不錯的穩定性。而其氧氣還原反應反應的提升可歸咎於多芳香族之網狀結構、quaternary (graphitic)-type nitrogen結構以及其配位結構。另外，原位X光吸收光譜分析也更進一步地了解其反應機制。

Non-precious metal catalysts of the oxygen reduction reaction (ORR) are highly favored for use in proton exchange membrane fuel cell (PEMFC) because of their relatively low cost. This study demonstrates the pyrolyzed M-corrole (M: Co, Fe) catalysts of the oxygen reduction reaction in PEMFC cathodes, with high catalytic performance. The py-Co-corrole/C at 700 °C exhibits the optimized ORR activity. The H2-O2 PEMFC using py-Co-corrole/C in the cathode reveals a maximum power density of 275 mW cm-2, which yields a higher performance and a lower metal loading than previous studies of Co-based catalysts for PEMFCs. The enhancement of the ORR activity of py-Co-corrole/C is attributed to the four-coordinated Co-corrole structure and the oxidation state of the central cobalt. While the py-Fe-corrole/C exhibits excellent ORR activity, via the direct four-electron reduction pathway, in the reduction of O2 to H2O, it is used in the H2-O2 PEMFC that produces high activity and excellent stability. By using the square wave voltammetry, the py-Fe-corrole/C perform a redox reaction of Fe(II)/Fe(III) at 0.6 V. Finally, the in-situ X-ray adsorption spectroscopy has been applied to determine the ORR mechanism of py-Fe-corrole/C.
Second work demonstrates carbon black-supported pyrolyzed vitamin B9 (folic acid) catalyst (py-Fe-FA/C) for the ORR in PEMFC. The ORR measurements reveal that py-Fe-FA/C shows an excellent ORR activity, via the direct four-electron reduction pathway. The H2-O2 PEMFC using py-Fe-FA/C in the cathode produces the maximum power density of 330 mW cm-2, with good stability. The enhanced ORR activity is attributed to the network structure of poly-aromatic hydrocarbons, the quaternary (graphitic)-type nitrogen and the coordination structure of the py-Fe-FA/C, as confirmed by the ORR mechanism study using the XPS and the in-situ X-ray adsorption spectroscopy.

摘要................................... I
Abstract .............................III
誌謝....................................V
Contents ..............................VI
List of Figures ...................... XI
List of Tables.......................XVIII
Chapter 1 Introduction .................1
1-1 Introduction of fuel cells .........1
1-2 Overview of PEM fuel cell...........8
1-3 Property for fuel cell application.......13
1-4 Polarization curve of fuel cell..........14
1-4 Principle of X-ray absorption spectroscopy .........16
Chapter 2 Literature Review............20
2-1 Important discovery of non-precious metal catalysts.....20
2-2 Recent research of non-precious metal catalysts.........25
2-3 Corrole-related study ...............................28
2-4 Idea from biological phenomenon......................30
2-5 Challenge to ORR.....................................31
Chapter 3 Motivation ....................................33
Chapter 4 Experimental Instruments ......................36
4-1 Chemicals and instruments............................36
4-2 Electrochemical measurements ........................39
4-3 Raman spectroscopy...................................42
4-4 X-ray photoelectron spectroscopy.....................43
4-5 X-ray absorption spectroscopy .......................44
4-6 In-situ XAS setup ...................................46
4-7 Fuel cell test.......................................47
Chapter 5 Synthesis of Corrole Derivatives as Cathode Catalysts for PEM
Fuel Cell Application ...................................49
5-1 Experimental.........................................49
5-1-1 General procedure for the synthesis of 5, 10, 15-triphenyl
corrole .................................................49
5-1-2 Synthesis of (triphenylphosphine) (5,10,15-triphenyl
corrolato) cobalt (III) .................................50
5-1-3 Synthesis of (nitrosyl) (5,10,15-triphenyl corrolato) iron
(III) ...................................................51
5-1-4 Preparations of pyrolyzed Co-corrole and pyrolyzed
VIII

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