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Author: 王家惠
Wang, Jia-Hui
Thesis Title: 碳質材料的表面改質與鑑定及其應用於水解生物質衍生之葡聚醣的研究
Surface Modification and Characterization of Carbonaceous Materials and its Application on Catalytic Hydrolysis of Biomass-derived Polysaccharides
Advisor: 鍾博文
Chung, Po-Wen
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2018
Academic Year: 106
Language: 英文
Number of pages: 95
Keywords (in Chinese): 碳質材料表面改質纖維素水解二氧化碳吸附
Keywords (in English): carbonaceous materials, surface modification, cellulose, hydrolysis, carbon dioxide adsorption
DOI URL: http://doi.org/10.6345/THE.NTNU.DC.066.2018.B05
Thesis Type: Academic thesis/ dissertation
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  • 本研究利用石油精煉所產出之廢棄碳質材料,介相瀝青(Mesophase pitch),經由各種化學表面修飾可以將酸性官能基團集中在其層狀結構邊緣上,已達到高的酸表面覆蓋率,且空間上鄰近的官能基可以仿纖維素水解酶上鄰近的羧酸基一般,有效水解纖維素的醣苷鍵斷鍵進而提高葡萄糖產率。以下本研究將使用四種不同的化學改質方式:(1)硫酸修飾(MP-SO3H)、(2)硫酸修飾再經水熱處理(MP-SO3H-HT)、 (3)硝酸修飾(MP-COOH)、(4)次氯酸鈉修飾(MP-Oxy)來合成酸性官能基化的碳質觸媒,並藉由表面分析來鑑定改質後之材料結構穩定度、酸性官能基團的組成等。由酸鹼反式滴定及元素分析計算表面的總酸量及不同酸性官能基團的組成,再藉由粉末X射線衍射計算材料的層間距離以及利用氮氣吸脫附測量材料的比表面積。另外,13C DP-MAS固態核磁共振光譜的分析中觀察到大部分的酸性官能基團位於sp2的碳上,因此可推論主要是在石墨納米結構邊緣上被改質。進一步將此一系列改質後的碳材用來做為水解纖維素的觸媒使用,在與纖維素(分子量約莫7,370 Da)的水解實驗中僅使用酸與纖維素的比例約4.8 mol%的催化劑(MP-SO3H)即可達到約44 mole %的高葡萄糖產率,再者由此催化劑上之酸性官能基團在水溶液中浸出(leaching)所造成的葡萄糖產率低於3 mole %,證實本研究設計之催化劑具有良好的穩定度以致於整個催化反應兼具環保與效率。
    除此之外,本研究意外發現在二氧化碳吸附的分析結果中,MP-SO3H-HT具有特別顯著的二氧化碳吸附量約為28 wt% (273K),由於本碳質材料為一層狀結構,有別於先前文獻所提到需具有孔洞及特定官能基之材料始具有的吸附能力,因此推論此一催化劑未來將有助於應用在二氧化碳吸附及封存。

    Herein, this study has discovered mesophase pitch (MP) carbonaceous material derived from petroleum waste, can be modified with high surface coverage of acid functional groups on the edges of layered structure, which could be further used as hydrolytic catalysts for hydrolyzing cellulose. This close proximity of acid moiety on aforementioned carbon materials resembles the center of hydrolysis enzymes, which composes of two close carboxylate groups, such as glycosidase. Chemical modification on carbon materials was listed as following: (1) sulfonic acid modification (MP-SO3H), (2) hydrothermal treatments of MP-SO3H (MP-SO3H-HT), (3) nitric acid modification (MP-COOH), and (4) sodium hypochlorite modification (MP-Oxy) and surface properties were characterized both qualitatively and quantitatively. Quantification of acid functionality was determined by the acid-base back-titration and the distance between layered structure was calculated from the powder X-ray diffraction pattern, and surface area can be characterized from nitrogen sorption study. Furthermore, acid groups were observed to be mainly modified on the edge of the graphitic nanostructure for MP structure owing to the diminishing of aliphatic carbon in spectra of 13C DP/MAS solid-state NMR analysis. In addition, hydrolytic performance was carried out by using MP-SO3H with a catalytic ratio of 4.8 mol% (acid groups/cellulose) for hydrolyzing cellulosic polymer of peak molecular weight (7,374 Da) and the results have shown the glucose yield can reach up to 44 mol%. On the other hand, only lower than 3 mol% of glucose yield could be observed during the hydrolytic reaction of leaching sulfonic groups and it further suggested that MP-based catalysts with acidic functionalities exhibited hydrolytically stable, which could lead the entire catalytic processes more effectively and eco-friendly.
    In addition, we serendipitously discovered that MP-SO3H-HT exhibited high carbon dioxide uptake upto 28 wt% and it might be attributed to layered structure of carbonaceous material, which was different from the adsorption energetics of porous materials reported previously. Hence, it suggested that this aforementioned carbon material can be potentially employed for the capture and storage of carbon dioxide in the future.

    List of Figures Ⅶ List of Tables Ⅹ Chapter 1 Introduction 1 1.1 Research Background 1 1.2 Introduction of Biomass 4 1.2.1 Cellulose 6 1.2.2 Hemicellulose 6 1.2.3 Lignin 7 1.3 Enzymes as a Catalyst for Hydrolysis of Cellulose 7 1.4 Hydrolysis of Lignocellulose Biomass into Oligosaccharides and Monosaccharides 12 1.4.1 Kinetics and Mechanism of Acid-Catalyzed Hydrolysis 13 1.4.2 Pretreatments of Crystalline Cellulose 13 1.4.3 Homogenous Catalysts for Hydrolysis of Cellulose 14 1.4.4 Heterogeneous Catalysts for Hydrolysis of Cellulose 14 1.5 Research Purpose 19 Chapter 2 Experimental 20 2.1 Chemicals and Reagents 20 2.2 Introduction of Instruments and Methods 21 2.2.1 Fourier-Transform Infrared Spectroscopy (FTIR) 21 2.2.2 Powder X-ray Diffraction (PXRD) 22 2.2.3 Thermogravimetric Analyzer (TGA) 23 2.2.4 Nitrogen Gas, Carbon Dioxide Gas and Water Vapor Sorption Analysis 24 2.2.5 Size-Exclusion Chromatography/Gel Permeation Chromatography (SEC/GPC) 26 2.2.6 13C Solid-state NMR (SSNMR) 28 2.2.7 High Performance Liquid Chromatography (HPLC) 29 2.2.8 Elemental Analysis (EA) 30 2.2.9 X-ray Photoelectron Spectroscopy (XPS) 31 2.2.10 Zeta Potential Measurements 32 2.2.11 Raman Spectrometer 33 2.2.12 Identification of Acid Sites Density (Boehm Titration) 34 2.3 Material Preparation and Treatment 36 2.3.1 Pretreatment of Raw Meso-phase Pitch 36 2.3.2 Functionalized Mesophase Pitch 36 2.4 Pretreatment of Cellulose 39 2.5 Hydrolysis of Cellulose 40 2.6 Leaching Test of Cellulose 41 2.7 Activation Energy Estimation of Cellobiose Hydrolysis 41 Chapter 3 Result and Discussion 44 3.1 Materials Characteristic 44 3.1.1 Result of the Condition Test for MP-COOH 44 3.1.2 Result of the Condition Test for MP-Oxy 56 3.1.3 Nitrogen Gas, Carbon Dioxide Gas and Water Vapor Sorption Isotherms 59 3.1.4 Identification of Acid Sites Density (Boehm Titration) 61 3.1.5 Powder X-ray Diffraction (PXRD) 63 3.1.6 Fourier-Transform Infrared Spectroscopy (FTIR) 64 3.1.7 Thermogravimetric Analysis (TGA) 65 3.1.8 13C Solid-state NMR (SSNMR) 66 3.1.9 Zeta Potential Measurements 68 3.1.10 X-ray Photoelectron Spectroscopy (XPS) 69 3.1.11 Raman Spectroscopy 70 3.2 Reactant characterization 71 3.2.1 X-ray Diffraction (XRD) 71 3.2.2 Fourier-Transform Infrared Spectroscopy (FTIR) 72 3.2.3 Thermogravimetric Analysis (TGA) 73 3.2.4 Size-Exclusion Chromatography/Gel Permeation Chromatography (SEC/GPC) 74 3.3 Result of Hydrolysis Reaction 76 3.3.1 Total Production of Cellulose Hydrolysis 76 3.3.2 Effect of Reaction Time on Amorphous Cellulose Hydrolysis 77 3.4 Result of Leaching Test 79 3.4.1 Leaching Test of MP-Oxy 80 3.5 Activation Energy Estimation of Cellobiose Hydrolysis 81 3.6 Comparison of Cellulose Hydrolysis Efficiency With Other Catalysts 82 Chapter 4 Conclusions 84 Chapter 5 References 86

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