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研究生： 蘇延善
To, Dien Thien
論文名稱： 銅基和鐵基氫化觸媒於二氧化碳氫化生產高附加價值化學品
Production of value-added chemicals by hydrogenation of carbon dioxide using copper- and iron-based catalysts
指導教授： 林裕川
Lin, Yu-Chuan
學位類別： 博士
Doctor
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2022
畢業學年度： 110
語文別： 英文
論文頁數： 72
外文關鍵詞： CO2 hydrogenation, copper phyllosilicate, iron carbides
相關次數： 點閱：68  下載：12 
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    • 使用銅基和鐵基催化劑，將二氧化碳分別轉化為CO，甲醇，或低碳鍊烯烴，證明利用可再生碳源生成加值化學品的潛力。本研究，提出不同催化劑以提高各相對應的反應催化性能。
    本研究使用胺基官能化銅鋅層狀矽酸鹽（Cu/Zn/SiO2-NH2）可獲得高選擇性的反向水煤氣變換反應（RWGS）。將 Cu/Zn/SiO2-NH2 與Cu/SiO2-NH2 和商業化銅鋅鋁催化劑 (CuZnAl2O3) 比較，Cu/Zn/SiO2-NH2不僅可以提高二氧化碳的轉化率，而且與未接枝的催化劑相比，還可以促進 RWGS 的選擇性（>99%）生成一氧化碳。通過二氧化碳程序升溫脫附 (CO2-TPD) 與紅外線吸收光譜 (DRIFTS) 分析結果表明，氨基官能化的銅基催化劑對二氧化碳有很強的化學吸附，這是由表面胺基與二氧化碳形成胺基甲酸酯所引起的。
    以碳-氮 (CN) 前驅物列如三聚氰胺、g-C3N4 (b-C3N4)與缺陷的g-C3N4 (d-C3N4)和硝酸鐵混合後通過共熱解法來合成Fe-CN-Py催化劑。在Fe-CN-Py催化劑中，Fe-d-C3N4-(0.3)-Py表現出最高的CO2轉化率(47.2%)、烯烴產率(10.8%)和烯烴空時產率 (STY, 4.5 微莫耳烯烴 秒-1 克鐡-1)。Fe-d-C3N4-(0.3)-Py的良好活性可歸功於其高度分散的碳化鐵，這是由d-C3N4的高非晶性和缺陷碳所引起的。Fe3+和d-C3N4之間的強交互作用抑制了團聚。另外本研究也建立了碳化鐵與烴類和烯烴的STY間的關聯性。

    Utilization and conversion of carbon dioxides to CO, methanol, or light olefins by using copper- and iron-based catalysts demonstrated a potential way to suppress carbon emission and product value-added chemicals from renewable carbon sources. In this study, tailoring catalysts to improve the catalytic performance of each respective reactions was proposed.
    Herein, a highly selective reverse water-gas shift (RWGS) can be obtained by using amino-functionalized Cu/Zn/SiO2 derived from zinc containing copper phyllosilicate (Cu/Zn/SiO2-NH2) was reported. Cu/Zn/SiO2-NH2 was compared with amino-functionalized Cu catalysts including copper phyllosilicate (Cu/SiO2-NH2) and copper/zinc supported on alumina (CuZnAl2O3). Cu/Zn/SiO2-NH2, not only can enhance the conversion of CO2, but also promote RWGS to yield CO with a high selectivity (>99%) comparing to their un-grafted counterparts. The role of the amino groups on the activity of amino-functionalized Cu-based catalysts was disclosed by various physicochemical characterization methods. The CO2-TPD and DRIFTS results showed a strong adsorption of CO2 on the amino-functionalized Cu-based catalysts caused by the formation of carbamate species.
    The mixture of carbon-nitrogen (CN) precursors such as melamine, bulky g-C3N4 (b-C3N4), or defective g-C3N4 (d-C3N4) and iron nitrate were used to synthesize Fe-CN-Py catalysts through the co-pyrolysis method. Among the Fe-CN-Py catalysts, Fe-d-C3N4-(0.3)-Py showed the highest CO2 conversion (47.2%), olefin yield (10.8%) and olefin space-time yield (STY, 4.5 μmol olefin s1 gFe1). The promising activity of Fe-d-C3N4-(0.3)-Py was attributed to its highly dispersed iron carbide, induced by the high amorphization degree and defective carbon of d-C3N4. The strong interaction between Fe3+ and d-C3N4 suppressed the extent of agglomeration. The correlation between iron carbides and the STY of hydrocarbons and olefins was established.

    Table of Contents Abstract i 摘要 ii Acknowledgement iii Table of contents iv List of Tables vi List of Figures vii List of Abbreviations ix Chapter 1 Introduction 1 Chapter 2 Synthesis of alcohols from hydrogenation of carbonates, carboxylic acids, carboxylates, formyls, and CO2 using copper phyllosilicates-derived catalysts: A review 2 2.1 Introduction 2 2.2 Formation of CuPS-cats 4 2.2.1 Synthesis methods 4 2.2.2 Effect of synthesis criteria 7 2.2.3 Effect of Supports 9 2.2.4 Promoter effects 11 2.2.5 CuPS nanotubes 11 2.3 Hydrogenation Activity of CuPS-Cats 17 2.3.1 Esters to alcohols 17 2.3.2 EC to MeOH and EG 19 2.3.3 Carboxylic Acid to Alcohol 19 2.3.4 Aldehyde to Alcohol 20 2.3.5 CO2 Hydrogenation to MeOH 21 2.4 Deactivation 21 2.4.1 Causes of deactivation 21 2.4.2 Remedial Actions 21 2.5 Prospective and challenges 22 Chapter 3 An investigation of the alkyl- and amino-functionalized CuZnPS for methanol synthesis from CO2 hydrogenation 23 3.1 Introduction 23 3.2 Experimental 24 3.2.1 Catalyst synthesis 24 3.2.2 Characterization 24 3.2.3 Activity evaluation 25 3.3 Result and discussion 25 3.3.1 Surface modification of CuPS, CuZnPS 25 3.3.2 Catalytic activity evaluation. 26 3.4 Conclusion 28 Chapter 4 Catalytic conversion of CO2 to light hydrocarbons by using iron carbides derived from iron nitrate co-pyrolyzing with melamine, g-C3N4, and defective g-C3N4 30 4.1 Introduction 30 4.2 Experimental 31 4.2.1 Synthesis of b-C3N4 and d-C3N4 31 4.2.2 Preparation of Fe-CN-Py catalysts 32 4.2.3 Characterization 32 4.2.4 Catalytic activity of Fe-CN-Py catalysts 33 4.3 Results and discussion 33 4.3.1 Synthesis of b-C3N4 and d-C3N4 33 4.3.2 Preparation of Fe-CN catalysts 34 4.3.3 CO2 hydrogenation performance 39 4.3.4 Post-reaction Fe-CN-(0.3)-Py catalysts 40 4.3.5 Structure-activity correlation 41 4.4 Conclusion 42 Support information 43 Chapter 5 Conclusion and recommendation 54 References 55 Appendices 70 Appendix 1. CV 70 Appendix 2. Publications 72

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