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研究生： 蘇芙蓉
Prameswari, Jedy
論文名稱： 透過解構工程催化劑調控二氧化碳氫化反應路徑: 鎳與銅及Silicalite-1與MCM-41載體之影響
Tuning CO2 Hydrogenation Pathways Via Exsolution-Engineered Catalysts: Effects of Nickel Vs Copper and Silicalite-1 Vs MCM-41 Supports
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： 2026
畢業學年度： 114
語文別： 英文
論文頁數： 132
中文關鍵詞： 二氧化碳氫化反應 、銅 、外析法 、鎳 、矽
外文關鍵詞： CO2 hydrogenation, Copper, Exsolution, Nickel, Silica
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    • 本研究探討以結構工程化二氧化矽載體觸媒進行二氧化碳氫化反應，聚焦於釐清金屬種類與孔洞結構如何調控觸媒結構、吸附行為與產物選擇性。結果顯示，析出之銅與鎳嵌入在 silicalite-1 (S-1）中，相較於以含浸製備之對照，其具有較高的一氧化碳選擇性與較低的一氧化碳生成活化能；值得注意的是，外析法可將原本傾向進一步氫化的 Ni 觸媒，轉變為更偏向（RWGS）的反應路徑，此結果歸因於析出表面所形成之獨特 Mex+-O-Si 界面物種、中等強度的路易士酸位點，以及較弱的一氧化碳吸附。其中，進一步比較微孔 S-1 與介孔 MCM-41 上鎳的析出行為，表明孔洞結構顯著影響析出結構：在受限的 S-1 微孔中，外析有利於形成 Ni-O-Si 的界面環境，使其具有較低的還原性與較高的路易士酸度，並進一步前弱了對一氧化碳的吸附強度。結果展現出一氧化碳的高選擇性並抑制甲烷化發生；相對地，MCM-41 具有較大的介孔削弱了此侷限效應，使其與含浸型觸媒之間僅呈現些微差異。In-situ DRIFTS 結果亦顯示，外析型觸媒會優先穩定單齒碳酸鹽物種，而含浸觸媒則傾向形成雙齒碳酸鹽物種，證實了外析法所誘發的侷限效應可有效調控二氧化碳氫化反應中的吸附能、表面中間體，以及與 RWGS 或甲烷化反應的選擇性。

    This thesis investigates CO2 hydrogenation over exsolution-engineered silica-supported catalysts, focusing on how metal identity and pore architecture regulate catalyst structure, adsorption behavior, and product selectivity. Exsolved Cu- and Ni-encapsulated silicalite-1 (S-1) catalysts exhibited higher CO selectivity and lower activation energies for CO formation than their impregnated counterparts, and notably, exsolution redirected intrinsically methanation-prone Ni toward a much more RWGS-selective pathway by generating unique Mex+-O-Si interfacial species, moderate Lewis acid sites, and weaker CO adsorption. Extending this concept, comparison of exsolved Ni catalysts on microporous S-1 and mesoporous MCM-41 showed that pore architecture strongly governs the consequence of exsolution: the confined micropores of S-1 promoted strongly anchored Ni-O-Si environments with lower reducibility, higher Lewis acidity, and weaker CO binding, resulting in high CO selectivity and suppressed methanation, whereas the larger mesopores of MCM-41 attenuated these effects and produced only modest differences relative to impregnated catalysts. In-situ DRIFTS further revealed that exsolved catalysts preferentially stabilized monodentate carbonate species, while impregnated catalysts favored bidentate carbonate species, confirming that exsolution-induced confinement is an effective strategy for tuning adsorption energetics, surface intermediates, and RWGS/methanation selectivity in CO2 hydrogenation over silica-supported catalysts.

    摘要 I Abstract II Acknowledgment III Table of contents V List of figures IX List of tables XII CHAPTER I 1 1.1 Motivation 1 1.2 Scope of this study 3 CHAPTER II 4 2.1 Exsolution in heterogeneous catalysis 4 2.1.1 Concept and fundamental principles 4 2.1.2 Structural electronic characteristics 5 2.2 CO2 hydrogenation 6 2.2.1 Thermodynamic and reaction network 6 2.2.2 Reverse Water Gas Shift (RWGS) 8 2.2.3 CO2 methanation 9 2.3 Reaction mechanisms and pathway selectivity 10 2.3.1 RWGS mechanism 10 2.3.2 CO2 methanation mechanism 11 2.3.3 Factors governing selectivity pathway 12 CHAPTER III 14 3.1 Chemicals 14 3.2 Catalyst preparation 15 3.2.1 Synthesis of exsolved Ni catalyst on silicalite-1 (Ni@S-1) 15 3.2.2 Synthesis of exsolved Cu catalyst on silicalite-1 (Cu@S-1) 15 3.2.3 Synthesis of impregnated catalyst on silicalite-1 15 3.24 Synthesis of exsolved MCM-41 catalyst 16 3.2.5 Synthesis of impregnated MCM-41 catalyst 16 3.3 Catalyst characterization 16 3.3.1 Bulk properties 16 3.3.2 Chemical properties 17 3.3.3 Activity evaluation 18 CHAPTER IV 19 4.1 Overview 19 4.2 Introduction 20 4.3 Experimental 21 4.3.1 Synthesis of Cu catalysts on silicalite-1 21 4.3.2 Catalyst characterization 21 4.3.3 Atomic structure construction 22 4.3.4 Density Functional Theory (DFT) calculation details 25 4.3.5 Charge density difference analysis 25 4.4 Results 26 4.4.1 Bulk properties 26 4.4.2 Chemical properties 31 4.4.3 Activity evaluation 37 4.4.4 Mechanistic study 43 4.4.5 DFT calculations 48 4.5 Discussion 51 4.6 Conclusion 53 CHAPTER V 54 5.1 Overview 54 5.2 Introduction 55 5.3 Experimental 56 5.3.1 Synthesis of Ni@S-1 and Ni/S-1 catalyst 56 5.3.2 Synthesis of Ni@MCM-41 and Ni/MCM-41 catalyst 56 5.3.3 Catalyst characterization 56 5.4 Results 58 5.4.1 Physical properties 58 5.4.2 Chemical properties 61 5.4.3 Activity evaluation 66 5.4.4 Mechanistic study 69 5.5 Discussion 71 5.6 Conclusion 73 CHAPTER VI 74 6.1 Summary 74 6.2 Future work and recommendation 76 REFERENCES 79 APPENDICES 98 APPENDIX A 99 APPENDIX B 117 List of publications 117 Curriculum vitae 118

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