調控雙金屬奈米觸媒組成和結構性質於二氧化碳還原反應之研究

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研究生：	Mulatu Kassie Birhanu Mulatu Kassie Birhanu
論文名稱：	調控雙金屬奈米觸媒組成和結構性質於二氧化碳還原反應之研究 Electrocatalytic Reduction of Carbon Dioxide Using Supported Bimetallic Electrocatalysts by Tuning the Composition and Structural Properties of Metal Nanoparticles
指導教授：	黃炳照 Bing-Joe Hwang
口試委員:	周澤川 Chou Tse-Chuan 鄧熙聖 Hsisheng Teng 林昇佃 Shawn D. Lin 黃炳照 Bing-Joe Hwang 蘇威年 Wei-Nien Su
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：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	205
中文關鍵詞：	合金化程度、表面組成、協同效應、中間物還原、雙原子奈米粒子、選擇性、封端劑
外文關鍵詞：	Alloying Extent, Surface Composition, Synergistic effect, Reduction Intermediate, Bimetallic Nanoparticles, Selectivity, Capping Agent
相關次數：	點閱：225 下載：0
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上一筆

隨著工業發展，車輛及工廠的二氧化碳排放量增加，而二氧化碳與氯氟烴(CFCs)、甲烷、臭氧、一氧化二氮皆為全球暖化原因。全球暖化所引發極地冰山融化、大氣升溫、人體健康成為日後研究發展方向，目前有許多二氧化碳減排方式，其中CO2的電化學還原(ECR)是這領域熱門研究之一。

於本篇研究中為探討關於雙金屬（銅基）的表徵及CO2電化學還原原理和反應機構對於產物生產效率和選擇性有顯著影響，在研究後段附有影響原因及相關補充資訊。文章重點主要在討論銅和銅基觸媒的催化活性以及優缺點比較，反應機制主要由單金屬銅觸媒和特定銅雙金屬合金觸媒在特定電解液、電位中分析產物濃度及法拉第效率和密度泛函理論（DFT）加以分析研究。在文獻回顧部分有對銅雙金屬合金觸媒的電化學還原機制及對於CO2還原產物生成加以討論，並開發具未來展望的雙金屬觸媒方式。在第一個實驗研究方法中，製備了Au/Cu雙金屬觸媒和單金屬奈米粒子觸媒應用於CO2電化學還原（ECR），並將觸媒與載體多壁奈米碳管（MWCNT）偶聯，能夠增強催化劑的導電性、電子轉移、催化活性和穩定性。而將金屬奈米粒子（NP）分散在親水性碳纖維紙上，目的是調整雙金屬和單金屬奈米粒子的電子結構和表面組成，透過調整表面與CO2間作用力來控制反應中間物。Au和Cu金屬之間的協同效應和合金化程度與MWCNT偶聯是增強活性和選擇性的主要關鍵，相對於RHE中低於-1.0V的電位下可達到接近70-80mA / cm 2的電流，而除了其它微量還原產物之外，在雙金屬觸媒上表現出約~78％的CO選擇性。通常情況下起始電位低於其他金屬電催化劑，表示法拉第效率和活性顯著增強。

第二項實驗中，使用Au/Cu奈米粒子（NPs）雙金屬電催化劑，依然用於CO2電化學還原（ECR）。將NPs沉積在功能化碳納米管（CNT）載體上，用於增加電流密度穩定性和導電性。製備方法則是與封端劑聚乙烯吡咯烷酮（PVP）混合，可提高還原產物活性和選擇性，原因為PVP可以調節電子結構間協同效應，包含金屬原子的結構性質，可抑制顆粒過度生長並防止NP聚集，這種由PVP控制AuCu顆粒尺寸的顯著降低和原子分散特性，結果提高了還原過程的催化速率及選擇性。最後藉由XAS分析研究PVP在NPs分散中的作用，通過在雙金屬表面上量測Au（111）和Cu（111）對PVP的吸附能，透過計算證明PVP的作用，將計算結果與不含PVP的雙金屬相比，使用PVP製備的電催化劑具有更好的活性和選擇性。相對於RHE -0.91 V下，AuCu / CNT（1.5g PVP）的CO產物法拉第效率（FE％）約為88％，但是在沒有PVP情況下約為~71％，結果表示含有PVP作用下可將FE％提高24％，並且與使用相同量的PVP單金屬電催化劑相比，雙金屬合金觸媒表現出更高活性和選擇性。

在另一項改質實驗中，我們合成出Au/Cu雙金屬NP並將其負載在TiO 2-C複合材料上，透過TiO 2和金屬NP之間的電子轉移可使得觸媒與載體間的偶聯增強，並且能夠在CO2電化學還原期間增加電催化劑的穩定性，而碳的作用則是增加電催化劑的電導率和表面積，以提高電催化還原CO 2的總反應活性。材料分析則是透過XRD、XAS、XPS、SEM、EDS等等量測儀器進行確認電催化劑和載體材料間表徵和可用性，最後使用電化學方式來測試還原活性，其中包括使用氣相色譜法(GC)與電化學圖譜分析還原產。

Emissions of CO2 from various types of industries, power plants, vehicles and many other factories are increasing and becomes one of the causes of global warming together with chlorofluorocarbons (CFCs), methane, ozone, nitrous oxide and others. Global warming provokes melting of polar ice, the increment of atmospheric temperature, expansion of dissertation and impact of human health. Even though there are different techniques for mitigation of CO2, electrochemical reduction (ECR) of CO2 is the interesting field of study for this work.

In the literature part of the thesis, basic ideas about characterizations of bimetallic (Cu-based), principles and mechanisms of electrochemical reduction of CO2 and descriptions to major and supplementary factors that significantly affect the reduction efficiency and selectivity of products are compiled coherently. The catalytic capability of Cu and Cu-based electrocatalysts and the advantages gained from Cu alloy over its monometallic are compared and discussed. The proposed reduction mechanisms, which are studied by several researchers based on experimental and density functional theory (DFT) approaches are compiled and analyzed. Reduction products and the corresponding faradaic efficiency using Cu monometallic and Cu-M bimetallic are identified at specific potential and concentration of electrolyte solutions. The literature part of this thesis addresses, understands of electrochemical reduction mechanisms and products of CO2 on Cu-based bimetallic catalysts and also provides an outlook for designing better bimetallic catalysts to obtain demanded products. Therefore, prior to the experimental work, this thesis provides an outlook for designing better bimetallic electrocatalysts to obtain selective products through ECR of CO2.

In the first experimental research approach, bimetallic and monometallic nanoparticles of Au and Cu are prepared for the electrochemical reduction (ECR) of CO2. Each electrocatalyst is supported and coupled with multi-walled carbon nanotubes (MWCNT), which able to enhance the conductivity, electron transfer, activity and the stability of the electrocatalyst. The supported metal nanoparticles (NPs) are loaded and dispersed on hydrophilic carbon fiber paper. The goal of this work is tuning the electronic structure and the surface composition of bimetallic and monometallic nanoparticles, which naturally manipulates the interaction between active sites and intermediate species of CO2. The synergistic effect between Au and Cu alloys and alloying extent with the coupling of MWCNT are the major contributions for enhanced activity and selectivity. Nearly 70-80 mA/cm2 of current was reached at a potential below -1.0 V vs. RHE and approximately up to ~78% of CO selectivity was obtained on the bimetallic composition in addition to other minor reduction products. Generally, faradaic efficiency and activity are significantly enhanced and the onset potential is comparatively lower than that of other metal electrocatalysts.

In the second work, bimetallic electrocatalysts of Au and Cu nanoparticles (NPs) are synthesized for electrochemical reduction (ECR) of CO2. The NPs are supported on a functionalized carbon nanotubes (CNT) to increase the stability and conductivity that resulted in high current density. To enhance the activity and selectivity of the reduction products, the preparation process was incorporated with capping agent i.e. Polyvinylpyrrolidone (PVP). Consequently, PVP can tune the synergistic (electronic and geometric) effects including the structural properties of the atoms, inhibit particle overgrowth and prevent the aggregation of NPs due to its steric hindrance effect. This scenario of varying the structural properties like a significant decrease of particle size and atomic distribution of AuCu are manipulated by PVP and results enhanced catalytic rate and selectivity of the reduction process. The role of PVP on the distribution of NPs have been investigated by XAS analysis and proved using computational calculations through the determination of adsorption energy of PVP with Au (111) and Cu (111) on the bimetallic surface. The electrocatalyst prepared with PVP has better activity and selectivity compared to the bimetallic synthesized without PVP. At -0.91 V vs. RHE the faradaic efficiency (FE%) of AuCu/CNT (1.5g PVP) is around 88% towards the formation of CO, but in the absence of PVP resulted in ~71%, indicates the existence of PVP increase the FE% by 24%. Bimetallic composition showed better activity and selectivity compared with its monometallic electrocatalyst using the same amount of PVP.

In the other alternative work, bimetallic NPs of Au and Cu are synthesized, which is supported on TiO2-C composites. The electron transfers between TiO2 and metal NPs makes the coupling between the catalyst and supporting material strong and able to enhance the stability of the electrocatalyst during ECR of CO2. The role of carbon is to increase the conductivity and surface area of the electrocatalyst and led to enhance the overall activity of the electrocatalytic reduction of CO2. Characterization of electrocatalysts and supporting materials are performed by XRD, XAS, XPS, SEM, EDS and using other characterization tools to confirm their property and its availability. The performance of the reduction activity has been performed by electrochemical test including determination of reduction products using gas chromatography hyphenated with electrochemical analysis.

                                                                                 Page
中文摘要                                                                       i
Abstract                                                                      iii
ACKNOWLEDGMENT                                                                   vi
TABLE OF CONTENTS                                                             viii
LIST OF FIGURES                                                                       xi
LIST OF SCHEMES                                                                     xvii
LIST OF TABLES                                                                xviii
NOMENCLATURE                                                                      xix
ABBREVIATIONS                                                                       xx
INTRODUCTION                                                                        1
1.    Background                                                                1
2.    Concise Overviews of Electrochemical Reduction of CO2                        4
3. Challenges of Electrochemical Reduction of CO2                                8
   PRINCIPLES AND REDUCTION MECHANISMS OF ELECTROCHEMICAL REDUCTION OF CO2    11
1.    Fundamental Parameters of ECR of CO2                                       11
2.    Intrinsic Factors and Role of Active sites of Electrocatalysts in ECR of CO2
14
2.1.    Electrochemical Surface Area (ECSA)                                       17
2.2.    Structure of catalyst surface                                               17
2.3.    Size of Nanocatalysts                                                       23
3.    Extrinsic/External Factors of ECR of CO2                               32
3.1.    Electrolyte Solution                                                       32
3.2.    Configuration of Electrochemical Cell                                       43
4.    Reduction Mechanisms and Selected Products of ECR of CO2 in Cu Based Bimetallic                                                                       46
4.1.    General Reduction Mechanisms of CO2                                       47
4.2.    Reduction Steps in the Formation of Main Products                       51
6.    Outlooks and Summary of Literature in ECR of CO2                       63
7.    Objectives and Motivation of the Study                                       66
7.1.    Objectives                                                               66
7.2. Motivation of the Study and Thesis Outline                               67
   EXPERIMENTAL AND CHARACTERIZATION SECTION                               69
1.    General Experimental Section                                               69
2.    Preparation of AuCu Nanoparticles Supported by Carbon Nanotubes          71
3.    Electrochemical Analysis in Reduction of CO2                               72
5. Preparation of Capping Agent Incorporated and Supported electrocatalyst       75
6. Characterization of AuCu bimetallic and Electrochemical Measurements       76
7. Preparation of TiO2/C powder                                               77
8. Characterization of Electrocatalyst and Electrochemical Performance Test       79
   ENHANCED ELECTROCATALYTIC REDUCTION OF CARBON DIOXIDE USING COPPER AND GOLD ALLOY NANOPARTICLES SUPPORTED BY CARBON NANOTUBES                               79
1. Introduction                                                               79
2. Results and Discussion                                                       81
2.1. Characterization of Electrocatalysts                                       81
2.2. Characterization of Electrocatalysts Using XAS                               86
2.3. Estimation of Alloying Extent                                               92
2.4. Performance of Electrochemical Reduction of CO2                               95
2.5. Determination and Discussions of Reduction Products                      100
3.  Summary                                                                      108
   SELECTIVE ELECTROCATALYTIC REDUCTION OF CARBON DIOXIDE BY TUNING THE STRUCTURAL PROPERTIES OF CARBON NANOTUBE SUPPORTED BIMETALLIC ELECTROCATALYST      110
1.    Introduction                                                              110
2.    Results and Discussion                                                      111
2.1.    Results of Characterized Electrocatalyst                              111
2.2. Evaluating Alloying Extent of Au and Cu                                      122
2.3.    Electrochemical Analysis in CO2 Reduction                              125
2.4.    Discussions to ECR of CO2 and Determination of Reduction Products      128
3.    Summary                                                                      131
   ELECTROCATALYTIC REDUCTION OF CARBON DIOXIDE USING GOLD AND COPPER BIMETALLIC SUPPORTED BY TITANIUM DIOXIDE AND ACTIVATED BY CARBON                              133
2.    Introduction                                                              133
3.    Results and Discussion                                                      135
3.3.    Characterization of Electrocatalyst                                      135
3.4.    Electrochemical Analysis and Discussions                              140
4.    Summary                                                                      142
   CONCLUSION AND PERSPECTIVES                                              143
REFERENCE                                                                      147
APPENDIX A: Supporting Data for Chapter 4                                      171
APPENDIX B: Supporting Data for Chapter 5                                      173
CURRICULUM VITAE (CV) OF THE AUTHOR                                              175

                                

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全文公開日期 2023/08/13 (校內網路)
全文公開日期 2025/08/13 (校外網路)
全文公開日期 2027/08/13 (國家圖書館：臺灣博碩士論文系統)

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