密度泛函理論計算探討氮氣活化機制於釕觸媒系統

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研究生：	楊凱翔 Yang, Kai-Shiang
論文名稱：	密度泛函理論計算探討氮氣活化機制於釕觸媒系統 Density Functional Theory Understanding of Nitrogen Activation Mechanisms by Ru Catalysts
指導教授：	陳馨怡 Chen, Hsin-Yi
口試委員:	陳仕元 Chen, Shih-Yuan 葉丞豪 Yeh, Chen-Hao 蔡明剛 Tsai, Ming-Kang 張鈞智 Chang, Chun-Chih
學位類別：	碩士 Master
系所名稱：	原子科學院 - 工程與系統科學系 Department of Engineering and System Science
論文出版年：	2022
畢業學年度：	110
語文別：	英文
論文頁數：	103
中文關鍵詞：	密度泛函理論、氮氣活化、釕、B5活性位點、氧化鎂(111) 、金屬-載體相互作用、氧溢流機制
外文關鍵詞：	DFT, Nitrogen activation, Ru, B5 active site, MgO(111), Metal -Support interaction, oxygen spillover
相關次數：	點閱：2 下載：0
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鑒於現今工業Haber-Bosch氨氣製程所需操作環境嚴峻(高溫450-500 °C及高壓30 MPa)，導致能源消耗占比過高及溫室氣體排放量過大。釕(Ru)基觸媒材料在產氨反應中最接近活化能-反應速率火山圖之頂點，亦即為一極有潛力於高活性觸媒，因此本研究之一將針對釕觸媒於製氨反應之主要速率決定步驟 - 氮氣活化進行原子尺度下之密度泛函理論(DFT)計算模擬，欲了解降低氮氣斷鍵活化能之主因，並探討釕觸媒中一特殊反應活性位點B5對活化反應之作用，比較一般表面與活性位點上氮氣活化機制的不同，於此此結果可提供實驗團隊於產氨之方向。此外，基於先前研究發現釕觸媒搭載於氧化鎂(111) ((Ru/MgO(111))之系統可有效解決氨氣製程中解離氫原子毒化觸媒材料表面之問題，本次研究也欲探討此Ru/MgO(111)觸媒於氮氣活化之效應，同時在Ru8觸媒團簇上結合B5活性位點，建構了類B5之Ru8，一來以檢測基載及氧溢流機制對於整體氮氣吸脫附行為的影響，二來測試基載對於團簇形成之活性位點有無效益，進而完善氮氣活化機制之探討及證明強金屬-載體相互作用(SMSI)對於催化反應的貢獻性。此DFT結果發現結合SMSI及類B5活性位點之Ru8MgO(111)觸媒對於氮氣活化有顯著降低N-N斷鍵活化能。

The capital and energy-intensive ammonia synthesis industry by the application of conventional iron-based catalysts prompts the tryout and the selection of ruthenium (Ru). Experiments on the corresponding employment had shown that the higher activity of Ru in the current Haber-Bosch process could be achieved with even milder operation conditions, which is beneficial for the development of minor-scale intermittent-operation-capability hardware units. Therefore, the study of the nitrogen activation, the rate-limiting step of the overall ammonia synthesis, on Ru is of all prominence. The comparison of the activation mechanism between the Ru terrace site and the B5 active site, the specific structure discovered in the synthesis, could give detailed insights into the catalysis, which could be exploited in future catalyst design and composite.
The preliminary data has further shown that the application of Ru catalyst on the MgO(111) system has demonstrated significant impacts on solving hydrogen poisoning, which could inhibit the subsequent synthesis of Ru. The extending study on the nitrogen activation by the system is the other goal of the work for a better understanding of the support and the oxygen spillover effect on the nitrogen sorption and activation behavior, and the investigation of B5-like structure construction on the system could determine the influence of the metal-support interaction on the active site, as well as the activity dependence of active site toward the support.

摘要    1
Abstract    2
Acknowledgment    3
Table of Contents    4
List of Figures    6
List of Tables    10
Chapter 1 Introduction    11
1.1 Current State of Ammonia Synthesis and Challenges    11
1.2 Objectives and Experiments Design    13
Chapter 2 Literature Review    16
2.1 Background of N2 activation in NH3 production    16
2.2 Selection of Ru Catalysts and Sabatier Principle    19
2.3 N2 Activation by Ru Catalysts    23
2.4 Alleviated Nitrogen Activation by B5 site    24
2.4.1 Discovery and Definition of B5 site    24
2.4.2 Effect of B5 Site on N2 Activation    30
2.5 Effect of Support on Assisting in N2 activation    31
Chapter 3 Methodology    35
3.1 Related Theory Introduction    35
3.1.1 First-Principles Calculations    35
3.1.2 Density Functional Theory (DFT)    37
3.1.3 Transition State Search    43
3.1.4 Bader Charge Analysis    46
3.2 Calculation Details    47
3.2.1 Convergence Test    47
3.2.2 Lattice Constant Optimization    50
3.2.3 Cohesive Energy, Binding Energy, and Adsorption Energy    52
3.2.4 Thickness Test For Surface Slab Model and Vacuum Layer    54
Chapter 4 Results and Discussion    57
4.1 Ru(0001) Terrace Model    57
4.1.1 N2 Dissociation    57
4.1.2 Coverage and Layer-Thickness Effects    62
4.2 Ru B5 Model    65
4.2.1 N2 Dissociation    65
4.2.2 DOS Analysis    69
4.3 Ru Clusters on MgO(111)    70
4.3.1 Ru1/MgO(111)    71
4.3.2 Ru4/MgO(111)    74
4.3.3 RuB5*/MgO(111)    79
4.4 Comparison of Ru(0001), B5, and Ru/MgO(111) Models    86
Chapter 5 Conclusions    89
Chapter 6 Prospect, Research, and Future works    90
Reference    91
Appendix    96
Appendix I : Detailed Introduction of Input and Output Files for VASP    96
Input Files    96
Output Files    98
INCAR Tag Setting    99
Appendix II : Interpretation of the Convergence Test    100

                                

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