以NiO/TiO2程序於紫外光照射下還原液相中二氧化碳至甲醇之研究

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研究生：	Truong Van Dai Hai Truong Van Dai Hai
論文名稱：	以NiO/TiO2程序於紫外光照射下還原液相中二氧化碳至甲醇之研究 Photocatalytic Reduction of Carbon Dioxide to Methanol in Aqueous Phase under UV Light Irradiation using NiO/TiO2
指導教授：	曾堯宣 Yao Hsuan Tseng 顧洋 Young Ku
口試委員:	曾堯宣顧洋蔣本基 Yao Hsuan Tseng
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	英文
論文頁數：	125
中文關鍵詞：	光催化程序、二氧化鈦、光還原二氧化碳、氧化鎳/二氧化鈦、甲醇
外文關鍵詞：	initial carbonate concentration, NiO/TiO2 film, photocatalytic reduction of CO2, initial solution pH
相關次數：	點閱：252 下載：20
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本研究利用氧化鎳以簡易溶膠凝膠法改質二氧化鈦，製備氧化鎳/二氧化鈦之複合型光觸媒，對液相之二氧化碳進行光還原反應。針對觸媒進行材料基本性質分析，分別探討氧化鎳摻雜濃度、溶液初始pH值、反應物的初始濃度對二氧化碳還原效率與甲醇產量的影響。
在實驗操作於較低的溶液pH值時，有利於二氧化碳還原效率。反應物的初始濃度增加，使水中的二氧化碳含量較多，也會提升二氧化碳轉化率和甲醇產量。實驗結果顯示，比較二氧化鈦、氧化鎳(10 wt%)/二氧化鈦和與氧化鎳(20 wt%)/二氧化鈦，摻雜氧化鎳之複合型光觸媒，可以有效阻止電子電洞對的再結合，提升光催化活性。摻雜的氧化鎳濃度越高，甲醇產量越高。
實驗中以碳酸鹽做為二氧化碳來源，在溶液初始濃度pH 4的操作條件下，照光後透過光觸媒進行光還原程序，將二氧化碳還原成甲醇。利用不同氧化鎳摻雜濃度合成之光觸媒，在紫外光照射下，進行5個小時的二氧化碳光還原反應，比較甲醇產量。實驗結果可得，二氧化鈦作為光觸媒進行光反應之甲醇產量為66.9 mg/L.gcatalyst，而以氧化鎳(20 wt%)/二氧化鈦為光觸媒的甲醇生產量為358.7 mg/L.gcatalyst，提升了5倍。

In this study, the NiO/TiO2 films were fabricated by incorporating NiO to TiO2 on glass substrates by a single impregnation method. In order to investigate the characterization of NiO/TiO2 photocatalysts, it were analyzed by various analysis instruments such as X-ray diffraction, field emission scanning electron microscope, UV-vis diffuse reflectance spectrometer and BET surface area analyzer. The effects of initial pH, coupled NiO dosage and initial carbonate concentration on the photocatalytic reduction of CO2 were studied. Compared with pure TiO2 photocatalysts, the prepared NiO/TiO2 film can significantly improve the photocatalytic efficiency under UV light irradiation.
The photocatalytic methanol-production activity of the prepared samples by reduction of CO2 was investigated using sodium bicarbonate as a precursor solution of CO2 in aqueous phase under UV light irradiation. The results suggested that an acidic system was favorable for the photocatalytic reduction process of CO2. Simultaneously, an increase of the initial carbonate concentration could increase the formation of methanol and conversion of carbonate in aqueous phase. As a result, a NiO loading significantly enhanced the methanol-production activity of TiO2 films. Under the UV light, TiO2 alone showed the productivity of methanol to be only 66.9 mg/L.gcatalyst at optimum conditions. Remarkably, the 10 wt% NiO loaded TiO2 photocatalyst shows maximum production of methanol up to 358.7 mg/L.gcatalyst after 5 hours of UV light irradiation at pH 4. The productivity increased by 5.4 fold when the NiO/TiO2 is used, which demonstrated that the role of doped NiO was significantly important for for enhancing the photocatalytic methanol evolution activity. At the optimal loading of 10 weight% NiO, NiO/TiO2 film showed the highest photocatalytic methanol-production activity. The relative order of photocatalytic reduction of CO2 in aqueous phase using different photocatalysts under UV light irradiation is NiO(10% weight)/TiO2 > NiO(20% weight)/TiO2 > TiO2.

Acknowledgement    I
中文摘要    III
Abstract    III
Table of Contents    V
List of Figures    IX
List of Tables    XIII
List of Symbols    XV
Chapter 1    1
Introduction    1
1.1 Background    1
1.2 Objectives and Scopes    2
Chapter 2    5
Literature Review    5
2.1 Photocatalytic Reduction of CO2    5
2.1.1 Fundamentals of Photocatalytic CO2 Reduction    5
2.1.2 Reaction Mechanism of Photocatalytic CO2 Reduction    7
2.1.3 Photoreactors for Photocatalytic Reduction of CO2 in Aqueous Phase    10
2.2 Photocatalyst for Photocatalytic Reduction of CO2    15
2.2.1 Titanium Dioxide    15
2.2.2 Titanium Dioxide-based Photocatalyst    16
2.2.3 Coupling Photocatalyst    19
2.2.4 Preparation of Photocatalyst    23
2.2.5 Development of Catalyst Supports for Photocatalytic CO2 Reduction    27
2.2.6 Performance Evaluation of Photocatalytic CO2 Conversion    29
2.3 Influence of Operating Factors on Photocatalytic CO2 Reduction in Liquid Phase    33
2.3.1 Effect of Reductant    33
2.3.2 Effect of Calcination Temperature    34
2.3.3 Effect of pH    35
Chapter 3    42
Materials and Experiments    42
3.1 Materials    42
3.2 Experimental Instruments and Apparatus    42
3.2.1 Experimental Instruments    42
3.2.2 Experimental Apparatus    43
3.3 Experimental Produces    45
3.3.1 Experimental Framework    45
3.3.2 Preparation of NiO/TiO2 Film    46
3.3.3 Characterization Analysis of NiO/TiO2 Photocatalyst    49
3.3.4 Photocatalytic Reduction of CO2 using NiO/TiO2 Films    54
Chapter 4    55
Results and Discussion    55
4.1 Background Experiments    55
4.1.1 Adsorption of CO2 on Photocatalysts in Liquid Phase    56
4.1.2 Photolysis of CO2 in Liquid Phase    56
4.1.3 Characterization of Initial TiO2 Powder    57
4.2 Characterization of Photocatalysts    59
4.2.1 Field Emission Scanning Electron Microscopy Analysis    59
4.2.2 X-ray Diffraction Analysis    64
4.2.3 UV-visible Diffuse Reflectance Spectra Analysis    65
4.2.4 Specific Surface Area Measurement    67
4.3 Photocatalytic Reduction of CO2 in Aqueous Phase using NiO/TiO2 Film    69
4.3.1 Effect of Initial pH    69
4.3.2 Effect of Initial Carbonate Concentration    74
4.3.3 Effect of NiO Dosage    78
4.4  Kinetic Analysis of CO2 Reduction in Liquid Phase using NiO/TiO2    82
Chapter 5    83
Conclusion and Recommendation    83
5.1 Conclusion    83
5.2 Recommendations    84
References    87
Appendix    96


                                

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