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研究生： 特斯法耶·阿拉米魯·德西
Tesfaye Alamirew Dessie
論文名稱： 用於混合水電解和電化學 CO2 還原應用的鉬基單原子電催化劑
Molybdenum based single atom electro-catalysts for hybrid water electrolysis and electrochemical CO2 reduction applications
指導教授： 黃炳照
Bing-Joe Hwang
口試委員: 黃炳照
Bing-Joe Hwang
蔡孟哲
Meng-Che Tsai
蘇威年
Wei-Nien Su
王迪彥
Di-Yan Wang
尼古斯·加比耶
Nigus Gabbiye
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： 98
中文關鍵詞： 碘化物耦合電化學水分解 、氮摻雜碳球上的單個鉬原子 、氫 、電化學二氧化碳減排 、四苯基卟啉鉬二聚體 、甲醇
外文關鍵詞： Iodide coupled electrochemical water splitting, Single molybdenum atom on nitrogen doped carbon sphere, Hydrogen, Electrochemical carbon dioxide reduction, Molybdenum tetra-phenyl porphyrin dimer, Methanol
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    • 電化學水分解產生氫氣和二氧化碳還原生產甲醇是滿足未來能源需求中最具吸引力及環保的策略。然而，這種電化學反應需要使用昂貴的貴金屬催化劑，這使得它們在工業應用中不符合需求。近年來，非貴金屬單金屬原子催化劑（SACs）因其在電化學水分解和二氧化碳還原應用中優秀的性能而越來越受歡迎。本文全面性地討論了碘化物結合水解離和二氧化碳還原反應中單原子鉬基催化劑的製備、表徵和催化性能。
    在第一項工作中，使用化學氣相沉積法，我們成功地將鉬單原子合成並分佈在有缺陷的氮摻雜碳球上（Mo-N4 / d-C），用於IOR結合產氫的應用。對於陽極端的碘氧化，Mo-N4/d-C 在0.77 V vs. RHE下即可達到10 mA cm-2的電流密度。在產氫端，該催化劑可生成0.1063 ml gcat-1 min-1的氫氣，法拉第效率為99.8%。此外，在DFT的研究中表明Mo-N4 / d-C結構可以促進碘化物氧化反應。
    在第二項研究中，我們成功開發了氧鉬四苯基卟啉二聚體（[O=Mo（TPP）]2O）催化劑，用於電化學二氧化碳還原為甲醇的應用。該催化劑能夠在 -1.0 V vs. RHE 下，在 0.1M HClO4中將二氧化碳轉化為甲醇，法拉第效率為 78%，電流密度為 50 mA cm-2。[O=Mo（TPP）]2O二聚體還能夠在-1.2 V vs. RHE下將二氧化碳轉化為乙醇，FE為45%。在電化學二氧化碳還原過程中，我們還進行了in-situ XAS和in-situ FTIR的研究，分別分析了催化劑結構的發展並了解反應的機制。理論研究中表明，[O=Mo（TPP）]2O二聚體結構有利於二氧化碳透過電化學轉化為甲醇。

    Electrochemical water splitting to produce hydrogen and CO2 reduction to produce methanol is the most attractive and environmentally benign strategies to satisfy the energy needs of the future. However, such electrochemical reactions require the use of expensive precious metal catalysts, which makes them impractical for industrial applications. Non precious single metal atom catalysts (SACs) have lately gained popularity owing to their superior performance in electrochemical water splitting and CO2 reduction applications. This thesis provides a comprehensive discussion of the preparation, characterization, and catalytic performance of single-atom molybdenum-based catalysts for iodide coupled water dissociation and CO2 reduction reactions.
    In the first work, using chemical vapor deposition technique, we successfully synthesized a single molybdenum atom distributed on a defective nitrogen carbon sphere (Mo-N4/d-C) for IOR-based hydrogen production application. For anodic iodide oxidation, the Mo-N4/d-C catalyst reaches a current density of 10 mA cm-2 at 0.77 V vs. RHE. This catalyst generates 0.1063 ml gcat-1 min-1 hydrogen with a Faradic efficiency of 99.8%. Furthermore, DFT studies show that the Mo-N4/d-C structure promotes iodide oxidation reaction.
    In the second work, we successfully develop oxy-molybdum tetraphenylporpherine dimer (([O=Mo(TPP)]2O) catalyst for electrochemical CO2 reduction to methanol application. This catalyst is able to convert carbon dioxide to methanol at -1.0 V vs. RHE in 0.1M HClO4 solution with 74 % FE and 50 mA cm-2 current density. The [O=Mo(TPP)]2O dimer is also capable of converting CO2 into CH3CH2OH with FE of 45% at -1.2 V vs. RHE. During the electrochemical CO2 reduction process, we also conduct in-situ XAS and in-situ FTIR to study the structural development of the catalyst and get mechanistic insight into the reaction respectively. It has been shown via theoretical studies that the [O=Mo(TPP)]2O dimer structure facilitates electrochemical conversion of CO2 to CH3OH.

    摘要..……………………………………………………………………………………………....i Abstract ii Acknowledgement iii List of figures vii Chapter 1: Introduction 1 1.1 General Background 1 1.2 Electrochemical water splitting 2 1.2.1 Current challenges of the electrochemical water splitting 4 1.3 Electrochemical reduction of CO2 4 1.3.1 Current challenges of the electrochemical carbon dioxide reduction to methanol 6 Chapter 2: Literature Review 7 2.1 Value-added water Electrolysis 7 2.1.1 Iodide oxidation reaction (IOR) 9 2.1.2 Amine oxidation reaction (AmOR) 15 2.1.3 Alcohol oxidation reaction (AOR) 17 2.1.4 Hydrazine oxidation reaction (HzOR) 19 2.1.5 Urea Oxidation Reduction (UOR) 21 2.2 Efficient catalysts for electrochemical CO2 to CH3OH conversion 24 2.2.1 Metal acetylacetonates 24 2.2.2 Metal Oxides 24 2.2.3 Metal-organic compounds 25 2.2.4 Pyridine electro-catalysts 26 2.2.5 Non-Metal electro-catalysts 26 2.2.6 Molybdenum-based catalysts 28 2.3 Single atom catalyst synthesis 29 2.3.1 Atomic layer deposition (ALD) 30 2.3.2 Electrochemical deposition (ECD) 31 2.3.3 Chemical vapor deposition method 31 2.3.4 Ball-milling method 32 2.4 Two-step doping method 33 2.4.1 Photo-chemical method. 33 2.4.2 Ion exchange method 34 2.5 Motivation and Objectives of the Study 36 2.5.1 Motivation 36 2.5.2 Objectives 37 Chapter 3: Experimental section and characterization 38 3.1 Chemicals and reagents 38 3.2 Single atom catalysts synthesis 39 3.2.1 Nitrogen doped carbon sphere (NCS) synthesis 39 3.2.2 Mo-N4/d-C electro-catalyst synthesis 39 3.2.3 [O=Mo(TPP)]2O electro-catalyst synthesis 40 3.3 Electrochemical Tests 40 3.3.1 Iodide oxidation electrochemical test 40 3.3.2 CO2 reduction electrochemical test 42 3.4 Characterization of Single-Atom Catalysts 43 3.4.1 High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy 43 3.4.2 X-ray Absorption Spectroscopy 43 3.4.3 Infrared Spectroscopy 45 3.4.4 X-ray Photoelectron Spectroscopy 45 3.4.5 X-ray powder diffraction 45 3.4.6 DFT calculations 45 Chapter 4: Efficient H2 Evolution coupled with Anodic Oxidation of Iodide over Defective Carbon-supported Single-atom Mo-N4 Electro-catalyst 46 4.1 Introduction 46 4.2 Results and Discussion 47 4.2.1 Characterization of Mo-N4/d-C single atom catalyst 47 4.2.2 Electrochemical IOR Performance 54 4.2.3 DFT calculations 58 4.2.4 Summary 60 Chapter 5: Electrochemical CO2 to methanol conversion through oxo -molybdenum tetra-phenyl-porphyrin dimer catalyst. 61 5.1 Introduction 61 5.2 Results and discussion 63 5.2.1 Synthesis and characterizations 63 5.2.2 Electrochemical performance 69 5.2.3 In-situ XAS Analysis 71 5.2.4 In-situ ATR-IR Spectroscopic Analysis 74 5.2.5 Post-reaction analysis 76 5.2.6 DFT Calculations 76 5.3 Summary 79 Chapter 6: Conclusions and perspectives 80 6.1 Conclusions 80 6.2 Future perspectives 81

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