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研究生： Kefale Wagaw Yizengaw
Kefale Wagaw Yizengaw
論文名稱： 銥參雜於氧空缺赤鐵礦表面對於二氧化碳與甲烷轉化之影響：密度泛函理論計算結合微觀動力學模擬研究
Theoretical Insights into Activation and Conversion of Methane and Carbon Dioxide over Single Iridium-Doped Hematite with Surface Oxygen Vacancy - A Combined DFT and Microkinetic Studies
指導教授： 江志強
Jyh-Chiang Jiang
口試委員: 江志強
陳良益
蔡明剛
江志強
江志強
學位類別： 博士
Doctor
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2023
畢業學年度： 111
語文別： 英文
論文頁數： 134
中文關鍵詞： 單原子摻雜 、赤鐵礦 、C-O耦合 、C-C耦合 、C-N耦合 、甲醇 、尿素 、催化劑回收 、氧空位
外文關鍵詞： Single atom doping;, Hematite, C–O coupling, C–C coupling, C–N coupling, Methanol, Urea, Catalyst recovery, Oxygen vacancy
相關次數： 點閱：243  下載：5 
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    • 二氧化碳和甲烷是廣為人知的溫室氣體，對全球變暖和氣候變化有顯著的影響。為了減緩其影響，將這些豐富的C1原料轉化為增值化學品至關重要。然而，現有的催化劑，主要是貴金屬氧化物，如二氧化銥，由於可行性限制而面臨商業化挑戰。克服高反應溫度、選擇性差、產率低和成本低效等障礙對於推進二氧化碳和甲烷轉換技術至關重要。
    為此，我提出了一種新的方法，其中包括開發一種低成本的催化劑，其性能與貴金屬氧化物相當，特別是IrO2（110）。這種創新的催化劑設計為，在赤鐵礦上進行了單金屬原子掺雜，產生具有單金屬氧空位的表面。通過密度泛函理論（DFT）計算和微觀動力學研究的結合，已經探索了其在甲烷、二氧化碳和氨吸附及共轉化中的催化活性。
    該研究的第一部分通過DFT + U方法探討了α-Fe2O3（110）和M/α-Fe2O3（110）表面（M = Ag、Ir、Cu或Co）上的甲烷活化。在這些表面中，Ir/α-Fe2O3（110）被證明是一種強效的C–H鍵催化劑，通過電子密度差異（EDD）、態密度（DOS）和Bader電荷計算確認了協同CH…O和Agostic相互作用。在Ir/α-Fe2O3（110）表面上增加氧空位（OV）顯示了能提高甲烷吸附能和C–H鍵活化，使其成為CH4脫氫的潛在催化劑。
    研究的第二部分探討了一種單銥原子掺雜和單氧原子缺陷赤鐵礦（110）表面催化劑。該催化劑具有同時活化二氧化碳和甲烷的能力，能進行直接C–O耦合。通過表面重分布表現出這種協同效應。微觀動力學研究強調了C–O耦合過程中氧缺陷位點上CH3*穩定性的作用。這些結果為催化劑設計最佳化帶來了希望。
    在隨後的研究中，我開發了一種催化劑表面的再生系統，解決了從二氧化碳和甲烷生產甲醇過程中的污染問題。該研究介紹了通過直接C–C耦合CO和CH2進行醋酸乙烯醇生產作為催化劑表面再生方法

    Carbon dioxide (CO2) and methane (CH4) are pivotal greenhouse gases, contributing significantly to global warming and climate change. To mitigate their impact, converting these abundant C1 feedstocks into value-added chemicals is crucial. However, existing catalysts, primarily noble metal oxides like iridium oxide (IrO2), pose commercialization challenges due to feasibility constraints. Overcoming obstacles such as high reaction temperatures, poor selectivity, low yields, and cost inefficiency is essential for advancing CO2 and CH4 conversion technologies.
    In response, a novel approach has been proposed involving a low-cost catalyst with comparable performance to noble metal oxides, specifically IrO2(110). This innovative catalyst design employs single metal atom doping on hematite, featuring a surface with a single atom oxygen vacancy. Through a combination of density functional theory (DFT) calculations and microkinetic studies, its catalytic activity in methane, carbon dioxide, and ammonia adsorption and co-conversion has been explored.
    The study's first segment scrutinizes methane activation on α-Fe2O3(110) and M/α-Fe2O3(110) surfaces (M = Ag, Ir, Cu, or Co) using the DFT + U method. Among these surfaces, Ir/α-Fe2O3(110) emerges as a potent catalyst for C–H activation, exhibiting cooperative CH…O and agostic interactions confirmed through electron density difference (EDD), density of states (DOS), and Bader charge calculations. Oxygen vacancy (OV) augmentation on the Ir/α-Fe2O3(110) surface demonstrates improved CH4 adsorption energy and C–H bond activation, rendering it a prime candidate for CH4 dehydrogenation.
    The second part of the study investigates a single iridium atom-doped and single oxygen atom-defect hematite (110) surface catalyst. This catalyst exhibits the capacity for direct C–O coupling by simultaneously activating CO2 and CH4. Synergistic effects of this simultaneous activation are evident through surface redistribution, with microkinetic studies underscoring the role of CH3* stability on the oxygen defect site during C–O coupling. These mechanistic insights hold promise for catalyst design optimization.
    In the subsequent study, a regeneration system for the catalyst surface is developed, addressing contamination issues during methanol production from CO2 and CH4. The study introduces direct C–C coupling of CO and CH2 for vinyl alcohol production as a catalyst surface regeneration approach.
    Finally, the thermocatalytic synthesis of urea and water from CO2 and ammonia is explored as a significant avenue. The study proposes the Ir/α-Fe2O3(110)-OV catalyst surface for urea production, highlighting promising performance. Urea desorption energy and C–N coupling barriers are evaluated, offering insights into sustainable urea synthesis with complete catalyst surface recovery.
    In summary, this research underscores innovative pathways for CO2 and CH4 conversion into value-added chemicals. By designing efficient catalysts and unraveling their mechanisms, the study contributes to advancing sustainable chemical synthesis processes.

    Table of Contents Theoretical Insights into Activation and Conversion of Methane and Carbon Dioxide over Single Iridium-Doped Hematite with Surface Oxygen Vacancy - A Combined DFT and Microkinetic Studies i Abstract 4 Acknowledgment 7 List of Figures 12 Index of Tables 14 List of Abbreviations 15 1.1 Background of the study 16 1.1.1. Methane and Carbon dioxide 18 1.1.2. Methane conversion 21 1.1.3. Carbon dioxide conversion 24 1.1.4. Methane and Carbon dioxide co-conversion 25 1.1.5. Hematite oxide 25 1.1.6. Iridium dioxide 28 1.1.7. Single atom catalysts (SACs) 29 1.1.8. Microkinetic simulation 31 1.1.9. Present study 35 Chapter 2. Remarkable performance of Single Iridium Atom Supported on Hematite for Methane Activation: Density Functional Theory Study 36 2.1. Introduction 36 2.2. Density Functional Theory Methods 37 2.2.1. Supercell approach 37 2.2.2. Brillouin zone sampling 38 2.2.3. Geometry Optimization 38 2.2.3. Finding the transition state 39 2.2.4. Vibration frequency calculation 40 2.2.5. Computational Details 40 2.2.6. Bulk model 43 2.2.7. Surface Model 46 2.3. Results and discussion 47 2.3.1. Methane adsorption on M/α-Fe2O3(110) surface (M =Ag, Ir, Cu, or Co) 47 2.3.2. Methane adsorption on Ir/α-Fe2O3(110)-OV surface 52 2.3.3. Electronic Properties Analysis 53 2.3.4. Methane activation on the α-Fe2O3(110), Ir/α-Fe2O3(110), and Ir/α-Fe2O3(110)-OV surfaces 56 2.4. Conclusions 59 Chapter 3: Theoretical Study of Co-Conversion of Carbon Dioxide and Methane on Single Iridium-Doped Hematite with Surface Oxygen Vacancy. 60 3.1. Introduction 60 3.2. Computational Details 61 3.3. Results and discussion 63 3.3.1. Carbon dioxide adsorption 63 3.3.2. Co-adsorption of CO2 and CH4 on Fe2O3 (110)-OV surface 66 3.3.3. Synergistic carbon dioxide and methane activation 68 3.3.4. Mechanistic investigation 70 3.3.5. Microkinetic analysis 76 3.4. Conclusions 80 Chapter 4: Deactivation and regeneration of an Ir-doped Fe2O3(110)-OV surface for methanol production from the co-conversion reaction of CO2 and CH4. 81 4.1. Introduction 81 4.2. Computational details 82 4.3. Results and discussion 84 4.3.1. Carbon monoxide desorption 84 4.3.2. Methane co-adsorption on Ir/α-Fe2O3(110)-OV surface 85 4.3.3. Mechanistic investigation 86 4.3.4. Microkinetic analysis 93 4.4. Conclusions 99 Chapter 5. Theoretical Study of C–N Bond Formation in Thermocatalytic Urea Production from Carbon Dioxide and Ammonia on Single Iridium-Doped Hematite with Surface Oxygen Vacancy 100 5.1. Introduction 100 5.2. Computational details 101 5.3. Results and Discussion 103 5.3.1. Ammonia and Carbon Dioxide Co-adsorption 103 5.3.2. Coupling of ammonia and carbon dioxide 105 5.3.3. The second ammonia Co-adsorption and urea synthesis 110 5.4. Conclusions 113 Chapter 6. Summary 114 6. Reference 117

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