臺灣博碩士論文加值系統

近年來，由於人口爆炸，能源部門的能源需求激增，造成石化燃料的枯竭並導致環境退化，溫室氣體甚至超出了我們可以控制的範圍。因此，有其必要性將石化燃料轉變為生物質的可再生能源進行生產。為了擴大應用範圍，生物質衍生碳可用於許多領域：能源應用，廢水處理，二氧化碳捕捉等，順帶一提，生物質衍生碳對抗生素的吸附性能受到較少關注。因此，本研究的目的是使用三種生物質廢物來源，創造具有高比表面積（SSA）和孔隙率的高端碳材料為多種應用。生物質衍生碳合成藉由熱解和活化兩步驟，後將合成材料將通過磺胺甲噁唑(SMX)吸附和超級電容器的兩個應用。結果表明，生物質衍生碳表現出高比表面積（2760m 2 / g-CF 8）、微孔體積（1.3cm 3 / g-CF 8），與具有優異的220 F / g的比電容。CF8之衍生碳電極也顯示出優異的功率和30.6 W h kg-1的能量密度。此外，含有大量官能團的RH8衍生碳對SMX吸附有最大Langmuir吸附容量（qm）為344mg / g。以上藉由偽一級、偽二級和粒子內擴散模型來評估吸附動力學，偽二階模型符合了實驗結果。此外，三種生物質衍生碳（CF8，SF8，RH8）的焓負值表明吸附過程是放熱性質。

The recent boom in energy demands from the energy sector due to population explosion has led to the depletion of fossil fuels that linked to environmental degradation, over-management of greenhouse gas. There is a need for a paradigm shift from fossil fuel for the renewable energy production of the biomass. For expansion of application, biomass-derived carbon can be used in many sectors: energy application, wastewater treatment, CO2 capture, etc. Incidentally, the adsorption property of biomass-derived carbon on antibiotics received a less attention. Hence, the purpose of this study is using three biomass wastes sources to create a high-end carbon material with high specific surface area (SSA) and porosity for multiple applications. Biomass-derived carbon have synthesized by two steps of pyrolysis and activation, then the as-synthesized materials will apply for two applications name by sulfamethoxazole adsorption and supercapacitor. The results show that the biomass-derived carbons exhibit a high SSA (2760 m2/g- CF8), micropore volume (1.3 cm3/g-CF8) that possessed an excellent of specific capacitance of 220 F/g in three electrode and 193.5 F/g in two electrode system. The CF8-derived carbon electrodes also shows excellent power capability and energy density of 31.25 W h kg-1 for power density of 7500 W kg-1. RH8-derived carbon which contents a lot of functional groups place a highest maximum Langmuir adsorption capacity (qm) for SMX adsorption of 344 mg/g. The adsorption kinetics was evaluated by pseudo-first-order, pseudo-second-order and intraparticle diffusion model. The pseudo-second-order model fitted the experimental results quite well. In addition, the negative value of enthalpy of three biomass-derived carbon (CF8, SF8, RH8) indicates the adsorption process is the exothermic nature.

中文摘要 i
ABSTRACT ii
ACKNOWLEDGEMENT iv
TABLE OF CONTENTS v
LIST OF FIGURES vii
LIST OF TABLES x
LIST OF ABBREVIATIONS xi
CHAPTER 1. INTRODUCTION 1
1.1. Motivation 1
1.2. Objectives 2
CHAPTER 2. LITERATURE REVIEW 3
2.1. Biomass-derived carbons and their potential applications 3
2.1.1. Sources of biomass and biomass-derived carbon preparation 3
2.1.2. Characteristics of different biomass-derived carbons 9
2.1.3. Application of biomass-derived carbons 14
2.2. Fate and transport of antibiotics and sulfamethoxazole 15
2.3. Removal technologies of antibiotics 19
CHAPTER 3. MATERIALS AND METHODS 21
3.1. Materials 21
3.2. Experimental 21
3.3. Synthesis of the biomass-derived carbon materials 22
3.4. Characterization techniques 24
3.4.1. Physicochemical properties 25
3.4.2. Electrochemical measurements 27
3.5. Sulfamethoxazole adsorption experiments 29
CHAPTER 4. RESULTS AND DISCUSSION 32
4.1. Characterization of biomass-derived carbon powders 32
4.2. Electrochemical capacitive performance 43
4.2.1. Three electrode system 43
4.2.2. Electrical double layer capacitors 52
4.3. Adsorption of Sulfamethoxazole onto different biomass-derived carbons 55
4.3.1. Effect of contact time on adsorption 55
4.3.2. Effect of adsorbent dosage on adsorption 56
4.3.3. Adsorption isotherms 57
4.3.4. Adsorption kinetic 65
4.4 Summary 71
CHAPTER 5. CONCLUSIONS 73
REFERENCES 75
APPENDIX 83

Sui, Q.; Cao, X.; Lu, S.; Zhao, W.; Qiu, Z.; Yu, G., Occurrence, sources and fate of pharmaceuticals and personal care products in the groundwater: a review. Emerging Contaminants 2015, 1 (1), 14-24.
2. Adams, C.; Wang, Y.; Loftin, K.; Meyer, M., Removal of antibiotics from surface and distilled water in conventional water treatment processes. Journal of environmental engineering 2002, 128 (3), 253-260.
3. Fatta-Kassinos, D.; Meric, S.; Nikolaou, A., Pharmaceutical residues in environmental waters and wastewater: current state of knowledge and future research. Analytical and bioanalytical chemistry 2011, 399 (1), 251-275.
4. Schafhauser, B. H.; Kristofco, L. A.; de Oliveira, C. M. R.; Brooks, B. W., Global review and analysis of erythromycin in the environment: Occurrence, bioaccumulation and antibiotic resistance hazards. Environmental Pollution 2018, 238, 440-451.
5. Rooklidge, S. J.; Miner, J. R.; Kassim, T. A.; Nelson, P. O., Antimicrobial contaminant removal by multistage slow sand filtration. Journal‐American Water Works Association 2005, 97 (12), 92-100.
6. Arico, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J.-M.; Van Schalkwijk, W., Nanostructured materials for advanced energy conversion and storage devices. In Materials For Sustainable Energy: A Collection of Peer-Reviewed Research and Review Articles from Nature Publishing Group, World Scientific: 2011; pp 148-159.
7. Miller, J. R.; Simon, P., Electrochemical capacitors for energy management. Science Magazine 2008, 321 (5889), 651-652.
8. Zhao, Y.; Liu, M.; Deng, X.; Miao, L.; Tripathi, P. K.; Ma, X.; Zhu, D.; Xu, Z.; Hao, Z.; Gan, L., Nitrogen-functionalized microporous carbon nanoparticles for high performance supercapacitor electrode. Electrochimica Acta 2015, 153, 448-455.
9. Zhang, L.; Liu, Z.; Cui, G.; Chen, L., Biomass-derived materials for electrochemical energy storages. Progress in Polymer Science 2015, 43, 136-164.
10. Abioye, A. M.; Ani, F. N., Recent development in the production of activated carbon electrodes from agricultural waste biomass for supercapacitors: a review. Renewable and sustainable energy reviews 2015, 52, 1282-1293.
11. Pickardt, C.; Neidhart, S.; Griesbach, C.; Dube, M.; Knauf, U.; Kammerer, D. R.; Carle, R., Optimisation of mild-acidic protein extraction from defatted sunflower (Helianthus annuus L.) meal. Food Hydrocolloids 2009, 23 (7), 1966-1973.
12. González-García, P., Activated carbon from lignocellulosics precursors: A review of the synthesis methods, characterization techniques and applications. Renewable and Sustainable Energy Reviews 2018, 82, 1393-1414.
13. Saidur, R.; Abdelaziz, E.; Demirbas, A.; Hossain, M.; Mekhilef, S., A review on biomass as a fuel for boilers. Renewable and sustainable energy reviews 2011, 15 (5), 2262-2289.
14. Ali, I.; Asim, M.; Khan, T. A., Low cost adsorbents for the removal of organic pollutants from wastewater. Journal of environmental management 2012, 113, 170-183.
15. Lewis, I., Chemistry of carbonization. Carbon 1982, 20 (6), 519-529.
16. Ioannidou, O.; Zabaniotou, A., Agricultural residues as precursors for activated carbon production—a review. Renewable and sustainable energy reviews 2007, 11 (9), 1966-2005.
17. Sevilla, M.; Mokaya, R., Energy storage applications of activated carbons: supercapacitors and hydrogen storage. Energy & Environmental Science 2014, 7 (4), 1250-1280.
18. Lu, H.; Zhao, X., Biomass-derived carbon electrode materials for supercapacitors. Sustainable Energy & Fuels 2017, 1 (6), 1265-1281.
19. Wang, J.; Kaskel, S., KOH activation of carbon-based materials for energy storage. Journal of Materials Chemistry 2012, 22 (45), 23710-23725.
20. Chiang, H.-L.; Huang, C.; Chiang, P., The surface characteristics of activated carbon as affected by ozone and alkaline treatment. Chemosphere 2002, 47 (3), 257-265.
21. Puziy, A.; Poddubnaya, O.; Socha, R.; Gurgul, J.; Wisniewski, M., XPS and NMR studies of phosphoric acid activated carbons. Carbon 2008, 46 (15), 2113-2123.
22. Oh, W.; Lim, C., Metal elimination effect by sulfuric acid for Ag and Cu pre-treated activated carbon. Journal of Ceramic Processing Research 2006, 7 (2), 95.
23. Navarro-Suárez, A. M.; Carretero-González, J.; Roddatis, V.; Goikolea, E.; Ségalini, J.; Redondo, E.; Rojo, T.; Mysyk, R., Nanoporous carbons from natural lignin: study of structural–textural properties and application to organic-based supercapacitors. RSC Advances 2014, 4 (89), 48336-48343.
24. Cazetta, A. L.; Vargas, A. M.; Nogami, E. M.; Kunita, M. H.; Guilherme, M. R.; Martins, A. C.; Silva, T. L.; Moraes, J. C.; Almeida, V. C., NaOH-activated carbon of high surface area produced from coconut shell: Kinetics and equilibrium studies from the methylene blue adsorption. Chemical Engineering Journal 2011, 174 (1), 117-125.
25. Din, A. T. M.; Hameed, B.; Ahmad, A. L., Batch adsorption of phenol onto physiochemical-activated coconut shell. Journal of Hazardous Materials 2009, 161 (2-3), 1522-1529.
26. Ranaweera, C.; Kahol, P.; Ghimire, M.; Mishra, S.; Gupta, R. K., Orange-Peel-Derived Carbon: Designing Sustainable and High-Performance Supercapacitor Electrodes. C 2017, 3 (3), 25.
27. Zhao, Y.; Fang, F.; Xiao, H.-M.; Feng, Q.-P.; Xiong, L.-Y.; Fu, S.-Y., Preparation of pore-size controllable activated carbon fibers from bamboo fibers with superior performance for xenon storage. Chemical Engineering Journal 2015, 270, 528-534.
28. Vukčević, M. M.; Kalijadis, A. M.; Vasiljević, T. M.; Babić, B. M.; Laušević, Z. V.; Laušević, M. D., Production of activated carbon derived from waste hemp (Cannabis sativa) fibers and its performance in pesticide adsorption. Microporous and Mesoporous Materials 2015, 214, 156-165.
29. Gokce, Y.; Aktas, Z., Nitric acid modification of activated carbon produced from waste tea and adsorption of methylene blue and phenol. Applied Surface Science 2014, 313, 352-359.
30. Gao, S.; Li, X.; Li, L.; Wei, X., A versatile biomass derived carbon material for oxygen reduction reaction, supercapacitors and oil/water separation. Nano Energy 2017, 33, 334-342.
31. Sudhan, N.; Subramani, K.; Karnan, M.; Ilayaraja, N.; Sathish, M., Biomass-derived activated porous carbon from rice straw for a high-energy symmetric supercapacitor in aqueous and non-aqueous electrolytes. Energy & Fuels 2016, 31 (1), 977-985.
32. Karnan, M.; Subramani, K.; Srividhya, P.; Sathish, M., Electrochemical studies on corncob derived activated porous carbon for supercapacitors application in aqueous and non-aqueous electrolytes. Electrochimica Acta 2017, 228, 586-596.
33. Bernardo, M.; Rodrigues, S.; Lapa, N.; Matos, I.; Lemos, F.; Batista, M.; Carvalho, A.; Fonseca, I., High efficacy on diclofenac removal by activated carbon produced from potato peel waste. International journal of environmental science and technology 2016, 13 (8), 1989-2000.
34. Du, W.; Sun, J.; Zan, Y.; Zhang, Z.; Ji, J.; Dou, M.; Wang, F., Biomass-derived nitrogen-doped hierarchically porous carbon networks as efficient absorbents for phenol removal from wastewater over a wide pH range. RSC Advances 2017, 7 (74), 46629-46635.
35. García-Mateos, F. J.; Ruiz-Rosas, R.; Marqués, M. D.; Cotoruelo, L. M.; Rodríguez-Mirasol, J.; Cordero, T., Removal of paracetamol on biomass-derived activated carbon: modeling the fixed bed breakthrough curves using batch adsorption experiments. Chemical Engineering Journal 2015, 279, 18-30.
36. Guo, Z.; Zhang, X.; Kang, Y.; Zhang, J., Biomass-derived carbon sorbents for Cd (II) removal: activation and adsorption mechanism. ACS Sustainable Chemistry & Engineering 2017, 5 (5), 4103-4109.
37. Shen, F.; Liu, J.; Zhang, Z.; Dong, Y.; Yang, Y.; Wu, D., Oxygen-rich porous carbon derived from biomass for mercury removal: An experimental and theoretical study. Langmuir 2018, 34 (40), 12049-12057.
38. Heberer, T., Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicology letters 2002, 131 (1-2), 5-17.
39. Santos, E. M.; Paull, G. C.; Van Look, K. J.; Workman, V. L.; Holt, W. V.; Van Aerle, R.; Kille, P.; Tyler, C. R., Gonadal transcriptome responses and physiological consequences of exposure to oestrogen in breeding zebrafish (Danio rerio). Aquatic Toxicology 2007, 83 (2), 134-142.
40. Yao, Y.; Gao, B.; Chen, H.; Jiang, L.; Inyang, M.; Zimmerman, A. R.; Cao, X.; Yang, L.; Xue, Y.; Li, H., Adsorption of sulfamethoxazole on biochar and its impact on reclaimed water irrigation. Journal of hazardous materials 2012, 209, 408-413.
41. Wu, Y.; Williams, M.; Smith, L.; Chen, D.; Kookana, R., Dissipation of sulfamethoxazole and trimethoprim antibiotics from manure-amended soils. Journal of Environmental Science and Health, Part B 2012, 47 (4), 240-249.
42. Rodríguez-Escales, P.; Sanchez-Vila, X., Fate of sulfamethoxazole in groundwater: Conceptualizing and modeling metabolite formation under different redox conditions. Water research 2016, 105, 540-550.
43. Liu, J.; Xu, R.; Zhang, C.; Song, W.; Zhang, N.; Jia, X.; Wang, H.; Sun, Q., Research on selected antibiotics removal from water through powder activated carbon adsorption. 2013; Vol. 5, p 578-582.
44. de Franco, M. A. E.; de Carvalho, C. B.; Bonetto, M. M.; de Pelegrini Soares, R.; Féris, L. A., Diclofenac removal from water by adsorption using activated carbon in batch mode and fixed-bed column: isotherms, thermodynamic study and breakthrough curves modeling. Journal of Cleaner Production 2018, 181, 145-154.
45. Sotelo, J. L.; Ovejero, G.; Rodríguez, A.; Álvarez, S.; Galán, J.; García, J., Competitive adsorption studies of caffeine and diclofenac aqueous solutions by activated carbon. Chemical engineering journal 2014, 240, 443-453.
46. Danmaliki, G. I.; Saleh, T. A., Effects of bimetallic Ce/Fe nanoparticles on the desulfurization of thiophenes using activated carbon. Chemical Engineering Journal 2017, 307, 914-927.
47. Sotelo, J.; Rodríguez, A.; Álvarez, S.; García, J., Removal of caffeine and diclofenac on activated carbon in fixed bed column. Chemical Engineering Research and Design 2012, 90 (7), 967-974.
48. Liu, B.; Zhang, L.; Qi, P.; Zhu, M.; Wang, G.; Ma, Y.; Guo, X.; Chen, H.; Zhang, B.; Zhao, Z., Nitrogen-doped banana peel–derived porous carbon foam as binder-free electrode for supercapacitors. Nanomaterials 2016, 6 (1), 18.
49. Datsyuk, V.; Kalyva, M.; Papagelis, K.; Parthenios, J.; Tasis, D.; Siokou, A.; Kallitsis, I.; Galiotis, C., Chemical oxidation of multiwalled carbon nanotubes. Carbon 2008, 46 (6), 833-840.
50. Ding, Z.; Hu, X.; Wan, Y.; Wang, S.; Gao, B., Removal of lead, copper, cadmium, zinc, and nickel from aqueous solutions by alkali-modified biochar: Batch and column tests. Journal of Industrial and Engineering Chemistry 2016, 33, 239-245.
51. He, X.; Ling, P.; Qiu, J.; Yu, M.; Zhang, X.; Yu, C.; Zheng, M., Efficient preparation of biomass-based mesoporous carbons for supercapacitors with both high energy density and high power density. Journal of Power Sources 2013, 240, 109-113.
52. Wu, M.-b.; Li, L.-y.; Liu, J.; Li, Y.; Ai, P.-p.; Wu, W.-t.; Zheng, J.-t., Template-free preparation of mesoporous carbon from rice husks for use in supercapacitors. New Carbon Materials 2015, 30 (5), 471-475.
53. Cheng, L.; Guo, P.; Wang, R.; Ming, L.; Leng, F.; Li, H.; Zhao, X., Electrocapacitive properties of supercapacitors based on hierarchical porous carbons from chestnut shell. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2014, 446, 127-133.
54. Fan, Y.; Liu, P.-F.; Yang, Z.-J.; Jiang, T.-W.; Yao, K.-L.; Han, R.; Huo, X.-X.; Xiong, Y.-Y., Bi-functional porous carbon spheres derived from pectin as electrode material for supercapacitors and support material for Pt nanowires towards electrocatalytic methanol and ethanol oxidation. Electrochimica Acta 2015, 163, 140-148.
55. Gao, F.; Shao, G.; Qu, J.; Lv, S.; Li, Y.; Wu, M., Tailoring of porous and nitrogen-rich carbons derived from hydrochar for high-performance supercapacitor electrodes. Electrochimica Acta 2015, 155, 201-208.
56. Weber, T. W.; Chakravorti, R. K., Pore and solid diffusion models for fixed‐bed adsorbers. AIChE Journal 1974, 20 (2), 228-238.
57. (a) Freundlich, H., Uber die adsorption in losungen. 1906; (b) Lagergren, S., Zur theorie der sogenannten adsorption geloster stoffe. Kungliga svenska vetenskapsakademiens. Handlingar 1898, 24, 1-39.
58. Sirés, I.; Brillas, E., Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: a review. Environment international 2012, 40, 212-229.
59. Ghaedi, M.; Ghaedi, A.; Abdi, F.; Roosta, M.; Vafaei, A.; Asghari, A., Principal component analysis-adaptive neuro-fuzzy inference system modeling and genetic algorithm optimization of adsorption of methylene blue by activated carbon derived from Pistacia khinjuk. Ecotoxicology and environmental safety 2013, 96, 110-117.
60. Vučurović, V. M.; Razmovski, R. N.; Miljić, U. D.; Puškaš, V. S., Removal of cationic and anionic azo dyes from aqueous solutions by adsorption on maize stem tissue. Journal of the Taiwan Institute of Chemical Engineers 2014, 45 (4), 1700-1708.
61. Budinova, T.; Savova, D.; Tsyntsarski, B.; Ania, C. O.; Cabal, B.; Parra, J. B.; Petrov, N., Biomass waste-derived activated carbon for the removal of arsenic and manganese ions from aqueous solutions. Applied Surface Science 2009, 255 (8), 4650-4657.
62. Shen, Y.-S.; Wang, S.-L.; Tzou, Y.-M.; Yan, Y.-Y.; Kuan, W.-H., Removal of hexavalent Cr by coconut coir and derived chars–The effect of surface functionality. Bioresource technology 2012, 104, 165-172.
63. Jia, Y.; Thomas, K., Adsorption of cadmium ions on oxygen surface sites in activated carbon. Langmuir 2000, 16 (3), 1114-1122.
64. Ahmed, M. J.; Theydan, S. K., Microporous activated carbon from Siris seed pods by microwave-induced KOH activation for metronidazole adsorption. Journal of Analytical and Applied Pyrolysis 2013, 99, 101-109.
65. Ho, Y.-S.; McKay, G., Sorption of dye from aqueous solution by peat. Chemical engineering journal 1998, 70 (2), 115-124.
66. Kuo, C.-Y.; Wu, C.-H.; Wu, J.-Y., Adsorption of direct dyes from aqueous solutions by carbon nanotubes: Determination of equilibrium, kinetics and thermodynamics parameters. Journal of Colloid and Interface Science 2008, 327 (2), 308-315.