臺灣博碩士論文加值系統

銅鉻氧化物因在許多化學反應中具有良好催化效果而受到密集的研究，可應用範圍十分廣泛。本實驗首次以靜電紡絲法製備出一維結構之銅鉻氧化物奈米纖維，並探討不同前驅液濃度、熱處理溫度、升溫速率及退火氣氛對其性質之影響。前驅液經電紡製程後，纖維以熱重量分析儀分析其熱分解行為，纖維經熱處理後以X光繞射分析儀分析結構、場發射式掃描電子顯微鏡觀察表面形貌並以比表面積分析儀量測纖維之比表面積。
本論文可分為兩大部分，第一部分為探討尖晶石型CuCr2O4電紡纖維之製備，由X光繞射分析儀分析結果可知，電紡絲在熱處理溫度600?C以上即可得CuCr2O4純相；由場發射式掃描電子顯微鏡分析表面形貌可知，快速升溫退火製程可抑制纖維燒結而使直徑降低；在700?C快速升溫退火20分鐘時，可得最低直徑為179.7奈米之CuCr2O4電紡纖維，其比表面積經量測可達8.32 m2/g。
第二部分為探討赤銅鐵礦CuCrO2電紡纖維之製備，比較各種無氧氣氛下退火後CuCrO2電紡纖維之相組成變化，由X光繞射分析儀及場發射式掃描電子顯微鏡分析結果可知，在真空環境下快速升溫退火，聚乙烯醇吡咯烷酮(PVP)分解氣氛可抑制尖晶石結構CuCr2O4相之生成，降低CuCrO2合成溫度，而在700?C得到CuCrO2之純相電紡纖維。合成之纖維可應用於甲醇蒸氣轉換產氫觸媒。

Copper-based catalysts are extensively studied due to their good catalytic performance in many applications such as steam reforming of methanol. In this work, one-dimensional Cu-Cr-O nanofiber fabricated via electrospinning method. It has been first demonstrated in present study. This experiment explored the effect of annealing temperature, heating rate, precursor concentration, and annealing ambient on fiber structure. The thermal decomposition behavior of the electrospun fiber was examined using a Thermogravimetric and Differential Thermal Analyzer. The crystalline phases of the fibers were identified using the theta-2thata X-ray diffraction meter and the morphology of fiber was studied by field emission scanning electronic microscope. Brunauer-Emmett-Teller method (BET) is used to measure the specific surface area of the fiber.
This work is divided into two main parts. First part is discussed the fabrication of CuCr2O4 fiber. The XRD analysis shows that the spinel CuCr2O4 fiber was obtained when the temperature was up to 600?C. Rapid thermal treatment can inhibit the sintering of the fiber and remain high aspect ratio. When the annealing time increased up to 15 min., single phase CuCr2O4 is formed. Furthermore, the fiber annealed at 700?C for 20 min. can obtained the thinnest diameter of 179 nm and the calculated maximum theoretical specific surface area is 4.13 m2/g, BET specific surface area was measured as 8.32 m2/g.
The second part discussed the annealing ambient in fabrication of CuCrO2 fiber. Annealing conditions, such as ambient gas and temperature, are investigated. The reducing atmosphere helps obtain the CuCrO2 phase thermodynamically hence CuCrO2 could be synthesized under a relatively low temperature. The experimental results show that the single-phase delaffosite CuCrO2 fiber was obtained after annealed in vacuum at 700?C for 20 minutes.

TABLE OF CONTENTS

摘 要 ii
ABSTRACT iv
TABLE OF CONTENTS vi
List of tables viii
List of figures ix
Chapter 1 Introduction 1
1.1 Cu-Cr-O composite 1
1.1.1 Spinel structure 1
1.1.2 Delafossite structure 3
1.2 Sol-gel processing 4
1.3 Electrospinning method 6
1.3.1 Evolution 6
1.3.2 Principle 6
1.3.3 Electrospinning of ceramic nanofibers 9
1.4 Methanol reforming 10
Reference 14
Chapter 2 Experimental details 19
2.1 Experimental reagents 19
2.2 Experimental gases 19
2.3 Precursor preparation 20
2.4 Instruments of electrospun fiber preparation 20
2.4.1 Electrospinning set up 20
2.4.2 Heat treatment of fibers 22
2.5 Characteristic analysis 23
2.5.1 Thermal decomposition behavior 23
2.5.2 Crystalline determination 24
2.5.3 Scanning electron microscope image observation 25
2.5.4 The specific surface area measurement 26
Chapter 3 Fabrication of CuCr2O4 fiber via electrospinning method 28
3.1 Introduction 28
3.2 Experiment 29
3.2.1 Preparation of CuCr2O4 precursor solution 31
3.2.2 Electrospinning process 31
3.2.3 Thermal treatment of CuCr2O4 fibers 33
3.2.4 Characterization techniques 34
3.3 Result and discussion 34
3.3.1 TGA curve of CuCr2O4 electrspun fiber 34
3.3.2 Annealing temperature of CuCr2O4 electrospun fibers 36
3.3.3 Effect of heating rate on fiber morphology 39
3.3.4 The effect of precursor concentration on fiber 44
3.4 Conclusions 47
3.5 Acknowledgement 47
Reference 48
Chapter 4 Fabrication of CuCrO2 fiber via electrospinning method 52
4.1 Introduction 52
4.2 Experimental 53
4.2.1 Preparation of CuCrO2 precursor solution 55
4.2.2 Electrospinning process 55
4.2.3 Thermal treatment of CuCrO2 fibers 57
4.2.4 The annealing ambient of CuCrO2 fibers 57
4.2.5 Two-step methods 59
4.2.6 Characterization techniques 60
4.3 Result and discussion 61
4.3.1 TGA curve of CuCrO2 electrspun fiber 61
4.3.2 Annealed in the air 64
4.3.3 Annealed in N2 66
4.3.4 Two-step annealed in forming gas (T-1) 70
4.3.5 Two-step annealed in the Air and N2 (T-2) 73
4.3.6 Annealed in vacuum 76
4.4 Conclusions 78
Reference 80
Chapter 5 Summary 82
Conference Presentations 84

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CHAPTER 3
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CHAPTER 4
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