臺灣博碩士論文加值系統

石墨烯為單層或少層石墨，其具有比矽高的電子遷移率與特殊的光學特性。因此可用於透明導電薄膜、染料敏化太陽能電池、超級電容器與其他複合材料的製備上。目前石墨烯的製備方法有化學氣相層積法、石墨氧化還原法與物理剝離法等。然而這些方法均無法量產石墨烯且其製程產生的副產物難以去除，因此目前石墨烯的市場機制尚未明確。本研究提出以生質碳進行酸浸漬裂解與催化裂解法製備高石墨烯含量的碳材料(GSCCMs)。
從研究結果發現所有炭材中均含有石墨烯片層，且可藉由XRD分析結果推導出石墨烯含量的定量方式並計算碳材中石墨烯含量。根據分析結果預估以生質碳製備所製備之理想石墨烯粉體的電阻值為0.01 Ω‧cm，此結果與市售以石墨氧化物進行還原所得之石墨烯粉體一致。以油棕果生質炭經CH3COOH浸漬後或以Na2O作為催化劑於於1500 oC進行熱裂解所製備的石墨烯純度分別可達83.86與82.88 %；平均導電度分別為84.690與78.985 S/cm。
從SEM分析中發現，石墨烯含量與生質物所含的α-纖維素含量有關，且添加Na2O在1500 oC進行熱裂解，其碳材表面會留下與石墨球型微晶大小相符的孔洞(約0.5 ~ 1 μm)。推測是由於α-纖維素因鈉離子的浸漬後在高溫形成的石墨微晶產生膨脹與分離的現象，因此在碳材料的製備中添加金屬氧化物作為催化劑將可製備出可調控尺寸的碳材料。而以純α-纖微素進行高溫裂解製備石墨烯碳材料，其石墨烯片層含量為93.01 %。且以自製的石墨烯碳材料製備之石墨烯氧化物薄膜具高溫相轉變的特性，且從結果顯示其平均相轉變的焓為9.41 J/g，較市售石墨所製備的石墨烯氧化物薄膜高出2.87倍。根據產業報導指出，目前人造石墨的價格為1,450 美元/噸，而石墨稀價格為28.57 美元/克。在本研究中生質炭與石墨稀炭材料之收率分別為31.46與23.44 %，其生產成本約為400元。因此利用生質碳製備之石墨烯碳材料與其氧化物薄膜可大幅降低開發成本。

Graphene is a monolayer graphite and has higher electron mobility than silicon, high heat conduction and special optical properties. It can be a potentially new semiconductor material and could be applied in transparent conductive thin film, dye-sensitized solar cells, super capacitors and composites. Many graphene manufacturing methods have been proposed, such as chemical vapor deposition, chemical reduction of graphene oxide and the exfoliation method. However, these processes are complicated by a high cost and the difficulty of removing byproducts. Therefore, the market mechanisms of graphene have not yet been established. In this study, we would like to propose a feasible method to characterize graphene sheet content quantitatively in carbon materials and processes for preparing high graphene sheet content carbon material (GSCCM) from biochar.
From our results, an empirical equation was found to calculate the graphene sheet content quantitatively in carbon-containing materials using an XRD spectrometer. Graphene sheet content, in a series of pyrolized biochar material powders, was calculated at a peak 2θ = 41° (d100) using XRD and resistivity measurement. The resistivity of ideal graphene powder was predicted to be 0.01 Ω‧cm, which was consistent with commercial reduced graphene oxide, and the highest graphene sheet content of GSCCMs from Elaeis biochar materials after CH3COOH impregnated through pyrolysis processes and catalytic pyrolized (added Na2O) is 83.86 and 82.88 %, respectively; its average conductivity is 84.690 and 78.895 S/cm, respectively.
From SEM analysis, the formation of graphene sheet related with α-cellulose content of woody biomass materials, and that with the processes of GSCCMs added to some metal oxides as catalysts, the graphite spherical grains and cytoskeleton surface of wood cells were separated leaving some holes by Na2O catalyst at 1500 oC, and the size (~ 0.5 to 1 μm) of the holes was similar to the graphite spherical grains. We conjecture that the Na2O catalyst can cause the swelling of graphite spherical grains at high temperatures (above 1500 oC), and the phenomenon might have resulted from the sodium impregnation of α-cellulose. Therefore, we can produce carbon materials with adjustable hole sizes through the addition of metal oxides as catalysts. With the production of GSCCMs from pyrolized α-cellulose powder, the graphene sheet content is 93.01 %.
The prepared GOPs from homemade graphene sheets contained carbon materials (GSCCMs) and evaluated the thermal properties of GSCCM derived GOPs. Results show that the GSCCM derived GOPs have high temperature phase transitions, and the average phase change enthalpy is 9.41 J/g, which is 2.87 times higher than graphite derived GOP. According to the industry reports, the cost of artificial graphite and graphene for the CVD process is 1,450 USD/ton and 28.57 USD/g, respectively. In this study, the yield of biochar and GSCCMs was 31.46 and 23.44 %, respectively. The production cost of GSCCMs was about 400 TND/ batch. Therefore, preparing GOP from GSCCMs could highly reduce the cost.

摘要 I
Abstract III
謝誌 V
Table of Contenets VI
List of Tables VIII
List of Figures X
Chapter 1 Introduction 1
Chapter 2 Literature Review 3
2.1 Biomass 3
2.1.1 Conversion technologies of biomass 4
2.1.2 Environmental impact of biomass 7
2.2 Carbon 8
2.2.1 Coal 11
2.2.2 Activated carbon 11
2.2.3 Biochar 13
2.2.4 Amorphous carbon 15
2.2.5 Carbon Black 18
2.2.6 Fullerene carbon 19
2.2.6.1 C60 20
2.2.7 Graphite 24
2.2.9 Graphene 29
2.2.10 Graphene oxide 32
Chapter 3 Materials and Methods 34
3.1 Materials 34
3.2 Equipments 35
3.3 Experimental 36
3.3.1 Preparation of biochar materials 37
3.3.2 Preparation of graphene sheet contented carbon materials 38
3.2.3 Preparation of graphene oxide solution (GOS) and graphene oxide paper (GOP) 40
3.2.4 Property analysis of samples 41
Chapter 4 Results and Discussion 47
4.1 Properties analysis of biochar materials 47
4.1.1 SEM/EDX analysis results 47
4.1.2 FT-IR analysis results 48
4.1.3 Conclusion remarks 49
4.2 Quantitative analysis of graphene sheet content in carbon materials 50
4.2.1 Properties analysis of GSCCMs 50
4.2.2 Relationship between the conductivity and graphene sheet conten 55
4.2.3 Conclusion remarks 59
4.3 Production of high graphene sheet contented carbon materials by catalytic pyrolysis method 60
4.3.1 Properties analysis of GSCCMs 60
4.3.2 Relationship between pyrolysis temperature, graphene fraction and conductivity of GSCCMs 79
4.3.3 Conclusion remarks 82
4.4 Production of high graphene sheet contented carbon materials by acid- impregnated pyrolysis method 83
4.4.1 Properties analysis of GSCCMs 83
4.4.2 Conclusion remarks 96
4.5 Relationship between the lignin, cellulose, hemi- cellulose and graphene sheet content by woody biomass 96
4.5.1 Conclusion remarks 100
4.6 Determination of graphene sheets content in carbon materials by Raman spectroscopy 101
4.6.1 Conclusion remarks 105
4.7 Preparation of graphene oxide solution and graphene oxide paper 105
4.7.1 Properties analysis of GOS and GOP 106
4.7.2 Conclusion remarks 114
4.8 Production cost of GSCCMs 114
Chapter 5 Conclusion 115
References 117
作者簡介 128

1. 王啟川、王運銘、朱博祥、曲新生、李君禮等人 編著，2007，2007年能源科技研究開發白皮書，經濟部能源局，臺北市，第116頁。
2. 行政院環保署統計資料，http://www.epa.gov.tw/。
3. 楊盛行、林正芳、王繼國，2003，廢棄物處理與再利用，國立空中大學，臺北縣，第87頁。
4. Tun#westeur040#, #westeur023#., Tanacı, H., and Aksu, Z., 2009, “Potential use of cotton plant wastes for the removal of remazol black B reactive dye,” Journal of Hazardous Materials, Vol. 163, pp. 187 - 198.
5. Dias, J. M., Alvim-Ferraz, M. C.M. Almeida, M. F., Rivera-Utrilla, J., S#westeur034#nchez-Polo, M., 2007, “Waste materials for activated carbon preparation and its use in aqueous-phase treatment: A review,” Journal of Environmental Management, Vol. 85, pp. 833 - 846.
6. Ngah, W. S. W. and Hanafiah, M. A. K. M., 2008, “Removal of heavy metal ions from wastewater by chemically modified plant wastes as adsorbents: A review,” Bioresource Technology, Vol. 99, pp. 3935 - 3948.
7. Mori, S., 2010, “A new complex plant for carbonization and composting of municipal wastes,” Particuology, Vol. 8, pp. 599 - 601.
8. Tai, H. S. and He, W. H., 2007, “A novel composting process for plant wastes in Taiwan military barracks,” Resources, Conservation and Recycling, Vol. 51, pp. 408-417.
9. Faaij, A., Ree R. V., Waldheim, L., Olsson, E., Oudhuis, A., Wijk, A. V., Daey-Ouwens, C. and Turkenburg, W., 1997, “Gasification of biomass wastes and residues for electricity production,” Biomass and Bioenergy, Vol. 12, pp. 387 - 407.
10. Huang, H. J., Ramaswamy, S., Al-Dajani, W., Tschirner, U. and Cairncross, R. A., 2009, “Effect of biomass species and plant size on cellulosic ethanol: A comparative process and economic analysis,” Biomass and Bioenergy, Vol. 33, pp. 234 - 246.
11. Huang, Y. P., Chien, C. C., Liou, Y. J., Huang, W. J. and Chang, T. Y., 2011, “Application of Mikania micrantha as an additive of high strength eco-materials,” Materials Science Forum, Vol. 685, pp. 161 - 168.
12. Chien, C. C., Lu, Y. S., Liou, Y. J. and Huang, W. J., 2012, “Application of waste bamboo materials on produced eco-brick,” Journal of Shanghai Jiaotong University, Vol. 17, pp. 380 - 384.
13. Novoselov, K. S., Geim, A. K., Morozov, S. V., Jiang, D., Zhang, Y., Dubonos, S. V., Grigorieva, I. V. and Firsov, A. A., 2004, “Electric field effect in atomically thin carbon films,” Science, Vol. 306, pp. 666-669.
14. Geim, A. K., 2009, “Graphene: Status and prospects,” Science, Vol. 324, pp. 1530-1534.
15. Campos-Delgado, J., Kim, Y. A., Hayashi, T., Morelos-G#westeur052#mez, A., Hofmann, M., Muramatsu, H., Endo, M., Terrones, H., Shull, R. D., Dresselhaus, M. S. and Terrones, M., 2009, “Thermal stability studies of CVD- grown graphene nanoribbons: Defect annealing and loop formation,” Chemical Physics Letters, Vol. 496, pp. 177 - 182.
16. 吳至彧，2009，利用化學氣相沉積法合成數層石墨烯以及其透明導電薄膜之研究，碩士論文，國立清華大學，工程與系統科學系，新竹市。
17. 呂俊頡、邱博文、黃昆平、張志振，2010，「以化學氣相沉積法成長大面積之單層石墨烯」，機械工業雜誌，第326期，第103 - 105頁。
18. 王革華、艾德生、馬振基 校訂，2008，新能源概論，五南圖書出版股份有限公司，臺北市，第56 - 83頁。
19. 姚向君、田宜水 編著、張勝雄、梁財春、張春田 編修，2008，生質能源-綠色黃金開發技術，新文京開發出版股份有限公司，臺北縣，第16 - 20、115 - 116、343 - 350頁。
20. Hustad, J. E., Skreiberg, #westeur025#. and S#westeur057#nju, O. K., 1995, “Biomass combustion research and utilisation in IEA countries,” Biomass and Bioenergy, Vol. 9, pp. 235 - 255.
21. Shen, L., Gao, Y. and Xiao, J., 2008, “Simulation of hydrogen production from biomass gasification in interconnected fluidized beds,” Biomass and Bioenergy, Vol. 32, pp. 120 - 127.
22. Bridgwater, A.V., 2012, “Review of fast pyrolysis of biomass and product upgrading,” Biomass and Bioenergy, Vol. 38, pp. 68 - 94.
23. Gunaseelan, V. N., 1997, “Anaerobic digestion of biomass for methane production: A review,” Biomass and Bioenergy, Vol. 13, pp. 83 - 114.
24. 梁大明、孫仲超、王彬、王琳、文芳等人 編著，2010，煤基炭材料，北京工業出版社，北京市，第1 - 3、54頁。
25. 賴耿陽，1991，碳材料化學與工學，復漢出版社，臺南市，第2 - 8、15 - 16、18 - 20、129 - 139頁。
26. 沈曾民，2006，新型碳材料，曉園出版社，臺北市，第1 - 7、19 - 23、29 - 31頁。
27. 稻垣道夫、大谷杉郎、大谷朝男 編著、賴耿陽 譯著，1994，碳材料與碳纖維工學，復漢出版社，臺南市，第13 - 14、38 - 41頁。
28. 經濟部工業局污染防治技術服務團，1994，工業廢水活性碳處理，工業污染防治技術手冊，經濟部工業局，臺北市，第7卷，第???頁。
29. 林文清，2007，微晶纖維素廢料之活性碳熱裂解資源化研究，碩士論文，國立中央大學，環境工程研究所，桃園縣。
30. 鄭慶堂，2004，以椰子纖維製備活性碳之研究，碩士論文，國立屏東科技大學，環境工程與科學系研究所，屏東縣。
31. Dias, J. M., Alvim-Ferraz, M. C. M., Almeida, M. F., Rivera-Utrilla, J. and S#westeur034#nchez-Polo, M., 2007, “Waste materials for activated carbon preparation and its use in aqueous-phase treatment: A review,” Journal of Environmental Management, Vol. 85, pp. 833-846.
32. Ahmad, A. A. and Hameed, B. H, 2010, “Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste,” Journal of Hazardous Materials, Vol. 175, pp. 298 - 303.
33. 合成工業原料股份有限公司，http://www.tophcc.com.tw/。
34. Ghosh, P. K., 2009, “Hexavalent chromium [Cr (VI)] removal by acid modified waste activated carbons,” Journal of Hazardous Materials, Vol. 171, pp. 116 - 122.
35. Wang, M., Hao, F., Li, G., Huang, J., Bao, N., and Huang, L., 2014, “Preparation of Enteromorpha prolifera-based cetyl trimethyl ammonium bromide-doped activated carbon and its application for nickel (II) removal,” Ecotoxicology and Environmental Safety, Vol. 104, pp. 254 - 262.
36. Ribas, M. C., Adebayo, M. A., Prola, L. D. T., Lima, E. C., Catalu#westeur050#a, R., Feris, L. A., Puchana-Rosero, M. J., Machado, F. M., Pavan, F. A. and Calvete, T., 2014, “Comparison of a homemade cocoa shell activated carbon with commercial activated carbon for the removal of reactive violet 5 dye from aqueous solutions,” Chemical Engineering Journal, Vol. 248, pp. 315 - 326.
37. Verheijen, F., Jeffery, S., Bastos, A. C., Velde, M. and Diafas. V., 2010, Biochar application to soils, JRC scientific and technical and reports, Joint research centre, Luxembourg, pp. 5-10.
38. Ogawa, M., 1994, “Symbiosis of people and nature in the tropics,” Farming Japan, Vol. 28, pp.10 - 34.
39. Chan, K.Y., Zwieten, L. V., Meszaros, I., Downie, A., Joseph, S., 2008, “Using poultry litter biochars as soil amendments,” Soil Research, Vol. 46, pp. 437 - 444.
40. Yamato, M., Okimori, Y., Wibowo, I. F., Ashori, S., Ogawa and M., 2006, “Effects of the application of charred bark of Acacia mangium on the yield of maize, cowpea and peanut, and soil chemical properties in South Sumatra, Indonesia,” Soil Science &; Plant Nutrition, Vol. 52, pp. 489 - 495.
41. Steiner, C., Das, K. C., Garcia, M., F#westeur055#rster, B. and Zech, W., 2008, “Charcoal and smoke extract stimulate the soil microbial community in a highly weathered xanthic Ferralsol,” Pedobiologia, vol. 51, pp. 359 - 366.
42. Asai, H., Samson, B. K., Samson, Stephan, H. M., Songyikhangsuthor, K., Homma, K., Kiyono, Y., Inoue, Y., Shiraiwa, T. and Horie, T., 2009, “Biochar amendment techniques for upland rice production in Northern Laos: 1. soil physical properties, leaf SPAD and grain yield,” Field Crops Research, Vol. 111, pp. 81 - 84.
43. Yu, X. Y., Ying, G. G. and Kookana, R. S., 2009, “Reduced plant uptake of pesticides with biochar additions to soil,” Chemosphere, Vol. 76, pp. 665 - 671.
44. Hartley, W., Dickinson, N. M., Riby, P. and Lepp, N. W., 2009, “Arsenic mobility in brownfield soils amended with green waste compost or biochar and planted with Miscanthus,” Environmental Pollution, Vol. 157, pp. 2654 - 2662.
45. Zhang, A., Cui, L., Pan, G., Li, L., Hussain, Q., Zhang, X., Zheng, J., and Crowley, D., 2010, “Effect of biochar amendment on yield and methane and nitrous oxide emissions from a rice paddy from Tai Lake plain, China,” Agriculture, Ecosystems &; Environment, Vol. 139, pp. 469 - 475.
46. Milla, O. M. V., 2013, Preparation and Plant-growth Efficiency Assessment of Biochars, Ph.D. Dissertation, National Pingtung University of Science and Technology, Department of Tropical Agriculture and International Cooperation, Pingtung.
47. Andrea, C. F., Robertson, J. 編著，譚平恒、李峰、成會明 譯，2007，碳材料的拉曼光譜-從奈米碳管道金剛石，化學工業出版社，北京市，第4 - 20、187 - 190頁。
48. Zeng, A., Neto, V. F., Gracio, J. J. and Fan, Q. H., 2014, “Diamond-like carbon (DLC) films as electrochemical electrodes,” Diamond and Related Materials, Vol. 43, PP. 12 - 22.
49. Chen, Y. T., Tsai, S. H. and Shei, H. J., 2012, “Application and analysis of DLC membrane heat transfer,” Journal of China University of Science and Technology, Vol. 153, pp. 43 - 59.
50. Niakan, H., Zhang, C., Hu, Y., Szpunar, J. A. and Yang, Q., 2014, “Thermal stability of diamond-like carbon- MoS2 thin films in different environments,” Thin Solid Films, In Press.
51. 暉盛科技股份有限公司，http://www.nemstek.com.tw/ch/film_2.htm。
52. Hasnat, M. A., Rashed, M. A., Alam, M. S., Rahman, M. M., Islam, M. A., Hossain, S. and Ahmed, N., 2010, “Electrocatalytic reduction of NO2−: Platinum modified glassy carbon electrode,” Catalysis Communications, Vol. 11, pp. 1085 - 1089.
53. Fu, Y., Lin, Y., Chen, T. and Wang, L., 2012, “Study on the polyfurfural film modified glassy carbon electrode and its application in polyphenols determination,” Journal of Electroanalytical Chemistry, Vol. 687, pp. 25 - 29.
54. Kroto, H. W., Heath, J. R., Obrien, S. C., Curl, R. F. and Smalley, R. E., 1985, “C(60): Buckminsterfullerene,” Nature, Vol. 318, pp. 162 - 163.
55. Kr#westeur037#tschmer, W., Lamb, L. D., Fostiropoulos, K. and Huffman, D. R., 1990, “C60: a new form of carbon,” Nature, Vol. 347, pp. 354 - 358.
56. 許明發、郭文雄 編著，2004，奈米碳管科技，國興出版社，新竹市，第1 - 3頁。
57. Hebard, A. F., Rosseinsky, M. J., Haddon, R. C., Murphy, D. W. and Glarum, S. H., 1991, “Superconductivity at 18 K in potassium- doped C60,” Nature, Vol. 350, pp. 600 - 601.
58. Bai, X., Wang, L., Wang, Y., Yao, W. and Zhu, Y., 2014, “Enhanced oxidation ability of g- C3N4 photocatalyst via C60 modification,” Applied catalysis B: Environmental, Vol. 152 - 153, pp. 262 - 270.
59. Iijima, S., 1991, “Helical microtubules of graphitic carbon,” Nature, Vol. 354, pp. 56-58.
60. 成會明，2004，奈米碳管，五南圖書出版股份有限公司，臺北市，第13 - 15、21 - 23、158、173頁。
61. Jin, Y. and Yuan, F. G., 2003, “Simulation of elastic properties of single- walled carbon nanotubes,” Composites Science and Technology, Vol. 63, pp. 1507 - 1515.
62. Zhou, O., Fleming, R. M., Murphy, D. W., Chen, C. H., Haddon, R. C., Ramirez, A. P. and Glarum, S. H., 1994, “Defects in Carbon Nanostructures,” Science, Vol. 263, pp. 1744 - 1747.
63. Satio, Y., Kawabata, K. K. and Matsumoto, T., 1996, “Carbon nanocapsules and single- layered nanotubes produced with platinum- group metals by arc- discharge,” Journal of Applied Physics, Vol. 80, pp. 3062 - 3067.
64. Ebbesen, T. W. and Ajayan, P. M., 1992, “Large- scale synthesis of carbon nanotubes,” Nature, Vol. 358, pp. 220 - 222.
65. Wu, D. H., Chien, W. T., Chen, C. S. and Chen, H. H., 2006, “Resonant frequency analysis of fixed-free single-walled carbon nanotube-based mass sensor,” Sensors and Actuators A, Vol. 126, pp. 117 - 121.
66. Kang, I., Heung, Y. Y., Kim, J. H., Lee, J. W., Gollapudi, R., Subramaniam, S., Narasimhadevara, S., Hurd, D., Kirikera, G. R., Shanov, V., Schulz, M. J., Shi, D., Boerio, J., Mall, S. and Ruggles-Wren, M., 2006, “Introduction to carbon nanotube and nanofiber smart materials,” Composites: Part B, Vol. 37, pp. 382 - 394.
67. 蔡宏傑，2004，以陰離子聚合法製備具聚苯乙烯接枝之奈米碳球複合材料，碩士論文，國立中正大學，化學工程研究所，嘉義。
68. Che, G., Lakshmi, B. B., Fisher, E. R. and Martin, C. R., 1998, “Carbon nanotubule membranes for electrochemical energy storage and production,” Nature, Vol. 393, pp. 346 - 348.
69. 張齡尹，2008，應用奈米二氧化鈦及奈米碳管於開發新穎處理含苯乙烯廢水及廢氣之聚合去除系統，碩士論文，國立屏東科技大學，環境工程與科學系研究所，屏東縣。
70. Karimi-Maleh, H., Tahernejad-Javazmi, F., Ensafi, A. A., Moradi, R., Mallakpour, S. and Beitollahi, H., 2014, “A high sensitive biosensor based on FePt/ CNTs nanocomposite/ N- (4- hydroxyphenyl)- 3, 5- dinitrobenzamide modified carbon paste electrode for simultaneous determination of glutathione and piroxicam,” Biosensors and Bioelectronics, Vol. 60, pp. 1 - 7.
71. 袁澄波、石作珉、陳汝翼 編著，1999，石墨材料之開發利用，復漢出版社有限公司，臺南市，第1-1 - 3、1-5、5-36 - 40頁。
72. Franklin, R. E., 1951, “Crystallite Growth in Graphitizing and Non-Graphitizing Carbons,” Proceedings of the Royal Society A, Vol. 209, pp. 196 - 218.
73. HARRIS, P. J. F., 2001, “Rosalind Franklin’s work on coal, carbon, and graphite” Interdisciplinary Science Reviews, Vol.26, pp. 204 - 210.
74. Hata, T., Vystavel, T., Bronsveld, P., DeHosson, J., Kikuchi, H., Nishimiya, K. and Imamura, Y., 2004, “Catalytic carbonization of wood charcoal: graphite or diamond?,” Carbon, Vol. 42, pp. 961 - 964.
75. Goodell, B., Xie, X. F., Qian, Y., Daniel, G., Peterson, M., Jellison, J., 2008, “Carbon nanotubes produced from natural cellulosic materials,” Journal of Nanoscience and Nanotechnology, Vol. 8, pp. 2472 - 2474.
76. Xie, X. F., Goodell, B., Qian, Y., Daniel, G., Zhang, D., Nagle, D. C., Peterson, M. L. and Jellison, J., 2009, “A method for producing carbon nanotubes directly from plant materials,” Forest Products Journal, Vol. 59, pp. 1 - 3.
77. Emmerich, F. G., Sousa, J. C., Torriani, I. L. and Luengo, C. A., 1987, “Applications of a granular model and percolation theory to the electrical resistivity of heat treated endocarp of babassu nut,” Carbon, Vol. 25, pp. 417 - 424.
78. 許斌、王金鋒 編著，2006，炭材料生產技術600問，冶金工業出版社，北京市，第309、311頁。
79. http://www2.lbl.gov/Science-Articles/Archive/sabl/2007/Nov/gap.html.
80. Sim, H. S., Kim, T. A., Lee, K. H. and Park, M., 2012, “Preparation of graphene nanosheets through repeated supercritical carbon dioxide process,” Materials Letters, Vol. 89, pp. 343 - 346.
81. Webb, M. J., Palmgren, P., Pal, P., Karis, O. and Grennberg, H., “A simple method to produce almost perfect graphene on highly oriented pyrolytic graphite,” Carbon, Vol. 49, pp. 3242 - 3249.
82. Stankovich, S., Dikin, D. A., Piner, R. D., Kohlhaas, K. A., Kleinhammes, A., Jia, Y., Wu, Y., Nguyen, S. T. and Ruoff, R. S., 2007, “Synthesis of graphene- based nanosheets via chemical reduction of exfoliated graphite oxide,” Carbon, Vol. 45, pp. 1558 - 1565.
83. Zheng, M., Takei, K., Hsia, B., Fang, H., Zhang, X., Ferralis, N., Ko, H., Chueh, Y. L., Zhang, Y., Maboudian, R. and Javey, A., 2010, “Metal- catalyzed crystallization of amorphous carbon to graphene,” Applied Physics Letters, Vol. 96, pp. 063110-1 - 063110-3.
84. Akhavan, O., 2010, “The effect of heat treatment on formation of graphene thin films from graphene oxide nanosheets,” Carbon, Vol. 48, pp. 509 - 519.
85. Chen, S., Zhu, J., Huang, H., Zeng, G., Nie, F. and Wang, X., “Facile solvothermal synthesis of graphene- MnOOH nanocomposites,” Journal of Solid State Chemistry, Vol. 183, pp. 2252 - 2257.
86. Liu, Z., He, D., Wang, Y., Wu, H. and Wang, J., 2010, “Graphene doping of P3HT: PCBM photovoltaic devices,” Synthetic Metals, Vol. 160, pp. 1036 - 1039.
87. Lee, Y. Bae, S., Jang, H., Jang, S., Zhu, S. E., Sim, S. H., Song, Y. I., Hong, B. H. and Ahn, J. H., 2010, “Wafer- scale synthesis and transfer of graphene films,” Nano Letters, Vol. 10, pp. 490 - 493.
88. Hong, W., Xu, Y., Lu, G., Li, C. and Shi, G., 2008, “Transparent graphene/ PEDOT - PSS composite films as counter electrodes of dye-sensitized solar cells,” Electrochemistry Communications, Vol. 10, pp. 1555 - 1558.
89. Zhou, H., Zhang, B., Zheng, J., Yu, M., Zhou, T., Zhao, K., Jia, Y., Gao, X., Chen, C. and Wei, T., 2014, “The inhibition of migration and invasion of cancer cells by graphene via the impairment of mitochondrial respiration,” Biomaterials, Vol. 35, pp. 1597 - 1607.
90. Hollanda, L. M., Lobo, A. O., Lancellotti, M., Berni, E., Corat, E. J. and Zanin, H., 2014, “Graphene and carbon nanotube nanocomposite for gene transfection,” Materials Science and Engineering: C, Vol. 39, pp. 288 - 298.
91. Sheshmani, S., Ashori, A. and Hasanzadeh, S., 2014, “Removal of acid orange 7 from aqueous solution using magnetic graphene/ chitosan: A promising nano- adsorbent,” International Journal of Biological Macromolecules, Vol. 68, pp. 218 - 224.
92. Liu, Q., Shi, L., Zeng, L., Wang, T., Cai, Y. and Jiang, G., 2011, “Evaluation of graphene as an advantageous adsorbent for solid- phase extraction with chlorophenols as model analytes,” Journal of Chromatography A, Vol. 1218, pp. 197 - 204.
93. 蘇清源，2011，「石墨烯氧化物之特性與應用前景」，物理雙月刊，第2期，第163 - 167頁。
94. Brodie, B. C., 1859, “On the atomic weight of graphite,” Proceedings of the Royal Society of London, Vol. 149, pp. 249 - 259.
95. Hummers, W. S. and Offeman, R. E., 1958, “Preparation of graphitic oxide,” Journal of the American Chemical Society, Vol. 80, pp. 1339 - 1339.
96. Luo, X., Robin, J. C. and Yu, S., 2004, “Effect of temperature on graphite oxidation behavior,” Nuclear Engineering and Design, Vol. 227, pp. 273 - 280.
97. Huh, S. H., Choi, S. H. and Ju, H. M., 2011, “Thickness- dependent solar power conversion efficiencies of catalytic graphene oxide films in dye- sensitized solar cells,” Current Applied Physics, Vol. 11, pp. S352 - S355.
98. Neri, G., Leonardi, S. G., Latino, M., Donato, N, Baek, S., Conte, D. E., Russo, P. A. and Pinna, N., 2013, “Sensing behavior of SnO2/ reduced graphene oxide nanocomposites toward NO2,” Sensors and Actuators B: Chemical, Vol. 179, pp. 61 - 68.
99. Min, Y. L., Zhang, K., Zhao, W., Zheng, F. C., Chen, Y. C. and Zhang, Y. G., 2012, “Enhanced chemical interaction between TiO2 and graphene oxide for photocatalytic decolorization of methylene blue,” Chemical Engineering Journal, Vol. 193 - 194, pp. 203 - 210.
100. Wang, F. and Zhang, K., 2011, “Reduced graphene oxide- TiO2 nanocomposite with high photocatalystic activity for the degradation of rhodamine B,” Journal of Molecular Catalysis A: Chemical, Vol. 345, pp. 101 - 107.
101. http://khvic.nsysu.edu.tw/khvic/JL/RAMAN.htm.
102. http://pic.npust.edu.tw/instrument.
103. Weast, R. C. and Astle, M. J., “CRC handbook of chemistry and physics,” CRC press Inc., Boca Raton city, pp. F-253 - F-260.
104. Zhao, B., Liu, P., Jiang, Y., Pan, D., Tao, H., Song, J., Fang, T. and Xu, W. 2012, “Supercapacitor performances of thermally reduced graphene oxide,” Journal of Power Sources, Vol. 198, pp. 423 - 427.
105. Alanyalıoğlu, M., Segura, J. J., Or#westeur052#-Sol#westeur041#, J. and Casa#westeur050#-Pastor, N., 2012, “The synthesis of graphene sheets with controlled thickness and order using surfactant-assisted electrochemical processes,” Carbon, Vol. 50, pp. 142 - 152.
106. Afanasov, I. M., Shornikova, O.N., Kirilenko, D. A., Vlasov, I. I., Zhang, L., Verbeeck, J., Avdeev, V. V. and Tendeloo G. V., 2010, “Graphite structural transformations during intercalation by HNO3 and exfoliation,” Carbon, Vol. 48, pp. 1858 - 1865.
107. Xie, X., Goodell, B., Qian, Y., Peterson, M. and Jellison, J., 2008, “Significance of the heating rate on the physical properties of carbonized maple wood,” Holzforschung, Vol. 62, pp. 591 - 596.
108. Sakaki, Y., Endo, T., Tanaka, N. and Inove, H., 2009, “Pre- treatment of lignocellulose biomass associated with the autoxidation of ethanol to acetal,” Green Chemistry, Vol. 11, pp. 27 - 30.
109. http://en.wikipedia.org/wiki/Cellulose.
110. http://en.wikipedia.org/wiki/Methyl_cellulose.
111. Brendel, O., Iannetta, P. P. M., and Stewart D., 2000, “A rapid and simple method to isolate pure alpha- cellulose,” Phytochemical analysis, Vol. 11, pp. 7 - 10.
112. 李洪麟、藍浩繁 編著，2006，生態材料實習，國立屏東科技大學，屏東縣，第527 - 530頁。
113. Roh, J. S., 2008, “Structural study of the activated carbon fiber using laser Raman spectroscopy,” Carbon Letters, Vol. 9, pp 127 - 130.
114. Cuesta, A., Dhamelincourt, P., Laureyns, J., Maertinez-Alonso, A. and Tascon, J. M. D., 1994, “Raman microprobe studies on carbon materials,” Carbon, Vol. 9, pp. 1523 - 1532.
115. Yang, M. H., Huang, W. J., Chien, T. C., Chen, C. M., Chang, H. Y., Chang, Y. S. and Chou, C., 2001, “Synthesis and thermal properties of diphenylsiloxane block copolymers,” Polymer, Vol. 42, pp. 8841 - 8846.
116. Unger, G., 1993, “Thermotropic hexagonal phase in polymers,” Polymer, Vol. 34, pp. 2050 - 2059.
117. 蔡伯達，2014，以濕式化學法自炭材中分離出石墨烯氧化物之研究，碩士論文，國立屏東科技大學，環境工程與科學系研究所，屏東縣。
118. http://big5.mofcom.gov.cn/gate/big5/price.mofcom.gov.cn/channel/priceinfo.shtml?prod_id=0111651.