高效能天然環氮錯合物-維他命B12應用於質子交換膜燃料電池陰極端之應用

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研究生：	張孫堂 Sun-Tang Chang
論文名稱：	高效能天然環氮錯合物-維他命B12應用於質子交換膜燃料電池陰極端之應用 High-performance Natural Electrocatalyst : Vitamin B12 for Oxygen Reduction Reaction in Polymer Electrolyte Fuel Cells
指導教授：	王丞浩 Chen-Hao Wang
口試委員:	陳貴賢 Kuei-Hsien Chen 林麗瓊 Li-Chyong Chen 吳紀聖 Jeffrey Chi-Sheng Wu 黃炳照 Bing-Joe Hwang
學位類別：	博士 Doctor
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2014
畢業學年度：	102
語文別：	英文
論文頁數：	116
中文關鍵詞：	氧氣還原反應、燃料電池、非貴金屬觸媒、維生素B12 、即時X光吸收光譜、阻抗分析
外文關鍵詞：	Oxygen reduction reaction (ORR), fuel cells, non-precious metal catalyst, Vitamin B12, in-situ XAS, impedance.
相關次數：	點閱：432 下載：0
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上一筆

本研究利用熱處理天然材料維生素 B12 (pyrolyzed Vitamin B12) 作為非白金觸媒取代白金觸媒應用質子交換膜燃料電池陰極端之研究。在本研究中，探討不同溫度熱處理對觸媒結構以及氧氣還原活性的影響，發現在熱處理溫度為700°C時氧氣還原活性為最佳，其電子轉移數為3.90，而產生的過氧化氫也僅有5%，再其次分別為900°C、500°C、300°C，其電子轉移數分別為3.57、3.42以及3.02，其過氧化氫比例分別為21.5%、29.0%、49.0%。利用Ｘ光繞射、Ｘ光吸收光譜、ＸＰＳ等表面結構鑑定以及分析，可以得知經過高溫熱處理的B12中間金屬鈷的氧化數由原本的3+轉變成2+，配位數也由原本的6配位轉變成4配位，這是由於經過高溫後，八面體的立體結構被破壞，轉換成一個非對稱的平面結構，這樣的結構由於結構以及能量障礙較小，氧氣分子容易接近觸媒表面並進行氧氣還原反應，所以氧氣還原能力佳，電子轉移數高以及觸媒活性好，在更高溫時，由於部分結構被熱裂解，中間Co-N4的結構被破壞與自身結構所含的磷形成Co2P，導致氧氣還原能力下降。此觸媒優越的地方還因為熱處理後結構中具有高比例的quaternary N-type nitrogen以及poly-aromatic hydrocarbons，這兩種結構幫助電子的傳導使得氧氣還原反應迅速，這些結構上的證明可由XPS、拉曼材料分析而得到。此外，電池的實際效能以及穩定性也是備受重視的，本研究利用維生素B12製備的陰極端觸媒應用在質子交換膜燃料電池上，其效能在0.5 V時可達370 mW cm-2，高於傳統的非白金觸媒CoTMPP/C以及Co/C作為陰極材料三倍以上，而穩定性測試也經過120小時不會減少，更加可以肯定此觸媒的優越性以及實用性。
除此之外，本研究還探討熱處理維生素B12氧氣還原反應機制，氧氣還原機制一直以來都是不確定，尤其是在非貴金屬觸媒中，因為結構複雜，因此分析起來也相對困難以及棘手。本研究利用即時同步輻射Ｘ吸收光譜搭配電化學儀器量測阻抗分析，可以清楚地得到熱處理的B12在進行氧氣還原時的機制以及現象，隨著反應電位的不同，阻抗分析的圖譜與X-ray吸收光譜也會隨著變化，加以證明氧氣如何與熱裂解的B12反應，這對往後非白金觸媒以及燃料電池的研究又更加邁向一大步。

In this study, pyrolyzed Vitamin B12, a material from nature, is used as a Pt-substitute catalyst in proton exchange membrane fuel cell (PEMFC) application. Here, non-precious metal catalysts using the pyrolyzed cyanocobalamin (Vitamin B12) supported by carbon blacks (py-B12/C) are investigated for oxygen reduction reaction (ORR). The optimal pyrolyzed temperature is 700°C, which shows an electron-transfer number of 3.90 and H2O2 yield of only 5% by using ring-rotating disk electrode technique. Other pyrolysis temperatures of 300°C (py-B12/C-300), 500°C (py-B12/C-500), and 900°C (py-B12/C-900) show that the electron-transfer numbers of py-B12/C-300, py-B12/C-500, and py-B12/C-900 are 3.02, 3.42, and 3.57, respectively. The H2O2 yield of 300°C (py-B12/C-300), 500°C (py-B12/C-500), and 900°C (py-B12/C-900), are 49.0%, 29.0% and 21.5%, respectively. Compared to pristine B12, the XRD patterns show the no obvious peaks for py-B12/C-300, py-B12/C-500 and py-B12/C-700, while py-B12/C-900 shows new peaks attributed to Co2P structure. The X-ray absorption spectra show that the Co oxidation state of py-B12-700 changed from Co (III) to Co (II), which indicates that the Co coordination number is changed from 6 to 4 during the pyrolysis. This suggests that py-B12-700 structure becomes a square-planar structure of Co-N4 chelate in the catalytic site. However, the Co-N4 chelate is decomposed with the increasing pyrolysis temperature to 900°C, leading to the loss of ORR activity. The ORR result of py-B12/C-700 shows high ORR activity because new structures are formed which are quaternary N-type nitrogen and poly-aromatic hydrocarbons after high temperature pyrolysis. For single cell test, the H2-O2 PEMFC that uses py-B12/C-700 in the cathode provides 370 mW cm-2 at 0.5 V, which yields the notably higher performance than py-CoTMPP/C and py-Co/C. High stability was maintained with no signs of decay after 120 hours of operation. The results reveal that pyrolyzed B12/C exhibits excellent activity and durability in the catalysis of the reduction of oxygen which is an important issue for the research of PEMFC.
Moreover, the in-situ XAS with impedance measurement is used to understand the mechanism of oxygen reduction reaction in this study. The method not only help us prove the mechanism of ORR in non-noble catalyst but also check the activity of the catalyst itself. In the analysis, the change of Co-N distance and impedance spectra are significant at various potential of reaction. The technique is very helpful in future researches of non-noble catalyst and fuel cells.

Contents
摘要	I
Abstract	III
Acknowledgements	V
Contents	VI
List of Figures	VIII
List of Tables	XV
Chapter 1 Introduction	1
1.1 Effects of global warming	1
1.2 The History of Fuel Cells	3
1.3	The Principle of PEMFC	7
1.4 The mechanism of ORR.	12
1-5 The Principle of X-ray Absorption	14
Chapter 2 Challenges and Literature Review	19
Chapter 3 Motivation	30
Chapter 4 Experimental Procedure	31
4.1 Flow Chart of Experiment	31
4.2 Chemicals and Instruments	33
4.3 Sample preparation and Instruments	35
Chapter 5 Result and Discussion	53
5.1 The activity of oxygen reduction	53
5.2 Characteristic of Py-B12: X-ray Diffraction (XRD)	59
5.3 Characteristic of Py-B12: X-ray Absorption (XAS)	61
5.4 Characteristic of Py-B12: X-ray photoelectron spectroscopy (XPS)	69
5.5 Raman spectroscopy	73
5.6 Accelerated durability test (ADT)	76
5.7 Single cell test	78
5.8 Stability test of single cell	82
5.9 In-situ XAS measurement with AC impedance spectroscopy	86
Chapter 6 Conclusion	98
Reference	100
 
List of Figures
Figure 1-1. (a) The mechanism of greenhouse and (b) the effect of greenhouse [1].	2
Figure 1-2. The principle of 1st fuel cell by William Grove developing [2].	5
Figure 1-3. The structure of PEMFC.	10
Figure 1-4. A typical polarization curve.	11
Figure 1-5. The possible model of ORR by Garten and Weiss’s assumption[10, 11].	12
Figure 1-6. Mechanism of O2 reduction on carbon nanotube surface[14].	13
Figure 1-7. The model of electron transfer pathway[13].	13
Figure 1-8: Transitions that contribute to XAS edges.	17
Figure 1-9: Three regions of XAS data	18
Figure 2-1. The structure of Heme.	20
Figure 2-2. The figure is Zelenay’s work in 2006. Polarization and power density plots for H2-O2 fuel cells with Co-PPY-C composite cathode (green lines) and polarization plot for the cell with Co/C cathode (red line). The Co loading is 0.06 mg cm-2; the cell temperature is 80°C[31].	22
Figure 2-3. The figure is Zelenay’s work in 2009. Volumetric current density of best NPMC in this work. Original polarization curves were obtained from H2-O2 fuel cell tests at 80°C and 100% relative humidity (RH) for cathodes made with the best NPMC in this work (small open circles, PO2 = PH2 = 1.5 bar)[47].	23
Figure 2-4. The figure is Zelenay’s work in 2011. Long-term stability test of a PANI-FeCo-C catalyst at a constant fuel cell voltage of 0.40 V (2.8 bar H2/2.8 bar air; 0.25 mgPt cm-2 anode; cell temperature 80°C)[48].	23
Figure 2-5. The model of Zhang’s assumption. Visualization of the reaction of porphyrin with carbon during the heat treatment[34].	25
Figure 2-6. Schematic configuration of a mechanically vibrating bed reactor. The schematic comes from Harnisch’s and Savastenko’s work [53, 54].	25
Figure 2-7. The structure of vitamin B12.	27
Figure 2-8. The possible mechanism of vitamin B12 is discussed by Zagal[60].	28
Figure 2-9. Mukerjee et al. discussed the proposed mechanism of ORR in non-noble catalyst[62, 63].	29
Figure 4-1. The flow chart of experimental procedure.	32
Figure 4-2. The schematic of experimental procedure.	37
Figure 4-3. The instrument of electrochemistry. Bio-logic VSP.	40
Figure 4-4. The half-cell and ring-rotating disk instrument.	40
Figure 4-5. The in-situ half-cell.	41
Figure 4-6. The instrument of beam line 01C2 (at the National Synchrotron Radiation Research Center, Hsinchu, Taiwan).	42
Figure 4-7. The instrument of Raman spectroscopy, Jobin-Yvon LabRAM HR800-Confocal micro-Raman spectroscope.	43
Figure 4-8. The optical layout of the 6m-HSGM. S means the radiation source. HFM and VFM are spherical mirrors. S1 and S2 are the entrance and exit slits, respectively. G is the grating. D is sample position.	45
Figure 4-9. The information of grating, photon energy and number of photons in beam line 20A.	46
Figure 4-10. The instrument of beam line 17C1 (at the National Synchrotron Radiation Research Center, Hsinchu, Taiwan).	49
Figure 4-11. The instrument of Fuel cell, FCED PD-50.	52
Figure 5-1. ORR curves for py-B12/C at various temperatures obtained by the RRDE technique in oxygen-saturated 0.1 M HClO4 solution at rotation rates of 1600 rpm and scan rates of 10 mV s-1.	55
Figure 5-2. (a) the electron-transfer number of the catalysts dependence on disk potentials; (b) the % H2O2 of the catalysts dependence on disk potentials.	56
Figure 5-3. ORR curves for py-B12/C, py-CoTMPP/C and Co/C obtained by the RRDE method in oxygen-saturated 0.1 M HClO4 solution at rotation rates of 1600 rpm and scan rates of 10 mVs-1.	57
Figure 5-4. (a) the electron-transfer number of the catalysts dependence on disk potentials; (b) the % H2O2 of the catalysts dependence on disk potentials.	58
Figure 5-5. XRD patterns of pristine B12 and py-B12 at various pyrolysis temperatures, the reference patterns of Vitamin B12 (JCPDS, PDF# 050029) and Co2P (JCPDS, PDF# 320306).	60
Figure 5-6. (a) XANES spectra for Co K-edge; (b) Fourier transforms of k3-weighted EXAFS data at Co K-edge.	64
Figure 5-7. The XANES spectra of P K-edge.	66
Figure 5-8. The assumption of structural changes during the pyrolysis.	68
Figure 5-9. The XPS spectra of (a) pristine B12, (b) py-B12-300, (c) py-B12-500, (d) py-B12-700, (e) py-B12-900.	71
Figure 5-10. The Raman spectra of (a) pristine B12, (b) py-B12-300, (c) py-B12-500, (d) py-B12-700, (e) py-B12-900.	74
Figure 5-11. The structure of a network structure of poly-aromatic hydrocarbons.	75
Figure 5-12. The ADT test of py-B12/C at 0.68 V (vs. RHE) for 100 h.	77
Figure 5-13. Polarization curves of the H2-O2 PEMFCs using py-B12/C-700, py-CoTMPP/C and Co/C as cathodes. Operation temperature: 70°C; Back pressure of H2 and O2: 1 atm; anode catalysts: 30 wt.% Pt/C with the metal loading of 0.25 mg cm-2 (E-TEK); electrolyte: NafionR 212 (H+, DuPont).	80
Figure 5-14. The performance of non-noble catalysts in recent 5 years [48, 51, 66, 94-97].	81
Figure 5-15. The 120-hours durability tests of H2–air PEMFC using py-B12/C, py-CoTMPP/C, and py-Co/C as the cathode at 0.40 V. The operation conditions of py-B12/C PEMFC: operation temperature: 70°C; Back pressure of H2 and air: 1 atm; anode catalysts: 40 wt% Pt/C with the metal loading of 0.25 mg cm-2 (E-TEK); electrolyte: NafionR 212 (H+, DuPont).	84
Figure 5-16. The 120-hours durability tests of H2–air PEFC using py-B12/C, Fe–N4/C[91], and Co–PPy/C[31] as the cathode at 0.40 V. The operation conditions of py-B12/C PEFC: operation temperature: 70°C; Back pressure of H2 and air: 1 atm; anode catalysts: 40 wt% Pt/C with the metal loading of 0.25 mg cm-2 (E-TEK); electrolyte: NafionR 212 (H+, DuPont).	85
Figure 5-17. The ORR curve by in-situ cell measurement. Scan rate: 1 mV/s, 0.1M H ClO4, Sat.O2, catalyst loading: 100 μg/cm2	89
Figure 5-18. The in-situ XANES with AC impedance spectroscopy at various bias: (a) XANES spectroscopy; (b) the absorption energy of py-B12 in Co K-edge.	90
Figure 5-19. The in-situ XAS with AC impedance spectroscopy at various bias: (a) impedance spectroscopy result; (b) XAS spectroscopy.	91
Figure 5-20. The in-situ XAS with AC impedance spectroscopy at 1.2 V vs. RHE: (a) impedance spectroscopy result; (b) EXAFS spectroscopy result.	92
Figure 5-21. The in-situ XAS with AC impedance spectroscopy at 1.0 V vs. RHE: (a) impedance spectroscopy result; (b) EXAFS spectroscopy result.	93
Figure 5-22. The in-situ XAS with AC impedance spectroscopy at 0.8~0.4 V vs. RHE: (a) impedance spectroscopy result; (b) EXAFS spectroscopy result.	94
Figure 5-23. The in-situ XAS with AC impedance spectroscopy at 0.2 V vs. RHE: (a) impedance spectroscopy result; (b) EXAFS spectroscopy result.	95
Figure 5-24. The assumption of model during oxygen reduction reaction.	97
 
List of Tables
Table 1-1. The information of 5 main types fuel cells [4, 5].	6
Table 4-1. The list of chemicals.	33
Table 4-2. The list of instruments.	34
Table 4-3. The optical parameters and grating information.	45
Table 5-1. Co K-edge E0 and Co oxidation state of pristine B12 and py-B12 at various pyrolysis temperatures calculated from Figure 5-6 (a).	65
Table 5-2. P K-edge E0 for B12 at various pyrolysis temperatures that calculated from Figure 5-7.	67
Table 5-3. The deconvolution results of XPS from Figure 5-9.	72
Table 5-4. The fitting results of impedance from Figure 5-18 (a).	96

                                

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