一維過渡金屬與其磷化物和三維過渡金屬硒硫化物在電解水產氫上的應用

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研究生：	曼尼 Arumugam, Manikandan
論文名稱：	一維過渡金屬與其磷化物和三維過渡金屬硒硫化物在電解水產氫上的應用 1D-Transition Metal/ Transition Metal Phosphide, and 3D-Transition Metal Dichalcogenide as Electrocatalyst for Hydrogen Evolution Reaction
指導教授：	闕郁倫 Chueh, Yu-Lun
口試委員:	韋光華 Wei, Kung-Hwa 林麗瓊 Chen, Li-Chyong 郭浩中 Kuo, Hao-Chung 邱博文 Chiu, Po-Wen
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2018
畢業學年度：	106
語文別：	英文
論文頁數：	69
中文關鍵詞：	產氫反應、水分解反應、電催化劑、過渡金屬、過渡金屬硫化物、過渡金屬磷化物
外文關鍵詞：	Hydrogen Evolution Reaction, Water Splitting, Electrocatalysts, Transition Metals, TMD, TMP
相關次數：	點閱：2 下載：0
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由於目前化石燃料會增長碳化合物的含量導致溫室效應，導致對於替代能源的需求和環境保護的意識越來越高，促使大眾開始致力發展環境友善與高效率能量轉換的方法來取代傳統燃料，而在眾多的方法中，利用電解水方法產氫和氧受到注目，它的優點在於低成本、容易架設以及高的轉換效率，在此方法中，決定了效率的因素主要在於催化劑的選擇，目前轉換效率最好的材料為鉑與其化合物，由於其特別的催化活性與高導電度，指他們擁有了較高的轉換電流密度(4.5 × 10-4 A cm-2)和較小的塔弗斜率(~40 mV/dec)，但是由於鉑為稀有金屬，其含量少、價格高，限制了其發展性與普及性，因此，大家開始尋找相對價格較低，又具有相當好的轉換效果的材料才取代鉑。在此篇論文中，我們開發了過度金屬的奈米線，過度金屬磷化物的奈米管和三維的過度金屬奈米花用來取代鉑，他們有著相當好的效果，例如:很小的過電位(<300 mV 在電流密度為10 mA/cm2)，相當小的塔弗斜率還有很高的穩定度，可以操作超過1000次，這些優異的性能主要由於三點；1. 石墨烯在奈米線的表面有很多缺陷，這些缺陷提供了很多活化的位置利於轉換2. 獨特的中空管狀的奈米線，能讓電解液能流入並在加入非晶碳增加導電度，提升效果3. 特別的奈米花形狀的金屬相二維材料提供了較高的體表面積比和活化位置。

Growing energy demands and environment consciousness due to current carbon-based fossil fuels have endorsed extensive research on the development of alternative energy conversion and storage technologies with high efficiency and environmental friendliness. Among them, electrochemical water splitting is very attractive, and is receiving more and more attention due to its low setting up cost, easy operation, and high yield. The critical challenge in this renewable technology is in dependency of highly active catalysts. To date, noble metal like platinum (Pt) and Pt-based materials are the efficient electrocatalysts for hydrogen evolution reaction (HER) because they exhibit incredibly high exchange current density (4.5 × 10-4 A cm-2) and smaller Tafel slope (~40 mV dec-1) owing to its high conductivity and remarkable catalytic properties. However, its scarcity on earth and high price limited it's extensive usage and gained insights towards finding the alternative high efficiency and low-cost electrocatalysts to approach the green, sustainable energy supply. To this end, we developed one dimensional (1D) nanowire and nanotube structure based on transition metal (TM) and transition metal phosphide (TMP), as well as three dimensional (3D) nanoflower based on transition metal dichalcogenides (TMD). The prepared materials exhibits superior electrocatalytic behaviour towards HER by achieving lower overpotentials < 300 mV at the current density of 10 mA cm-2 with low Tafel slopes and excellent stability over 1000 cycles. These superior electrocatalytic performances are due to (1) presence of graphene at the surface of nanowires increases the active sites by its defective edges, (2) easy diffusion of electrolyte by helical nanotube structure as well as increase in conductivity by the amorphous carbon, and (3) higher active sites due to high surface area of nanoflower morphology and metallic 1T phase of TMD.

Chinese Abstract                                                i
English Abstract                                               ii
Acknowledgements                                              iii

Chapter 1 Introduction
1 Hydrogen - a clean and green energy source                  1
2 Water Electrolysis                                          2
2.1 HER mechanism in acidic and alkaline media                3
2.2 Evaluating performance of HER catalysts                   4
3 Literatures Review                                          6

Chapter 2 Experiments
1 Synthesis of Copper nanowire                               10
1.1 Electrode fabrication for HER                            10
1.2 Growth of Graphene carbon-enclosed chemical vapor
deposition (CE-CVD)                                            10

1.3 Harsh environments test                                  12
2 Synthesis of Copper phosphide helical nanotubes            12
3 Synthesis of (1T/2H) MoS2/MoO3 nanoflowers                 13
4 Material Analysis and Characterization                     13
4.1 Scanning Electron Microscope (SEM)                       14
4.2 Transmission Electron Microscope (TEM)                   14
4.3 X-ray diffraction spectrometer                           14
4.4 Raman Spectrometer                                       14
4.5 X-ray photoemission spectrometer and Ultraviolet
photoelectron Spectroscopy                                     15

4.6 Electrical measurements                                  15
4.7 Surface area measurements                                15
4.8 Sea water analysis                                       15
4.9 Electrochemical hydrogen evolution reaction              15

Chapter 3 Transition Metal (Cu) as Electrocatalyst
1 Why Cu is not an efficient electrocatalyst for HER?        17
2 Structural and crystallinity evidence of as synthesized
Cu NWs                                                         17
3 Optimization of graphene growth by CECVD process           19
4 Identification of stability towards high harsh environments 22
4.1 Basic test (0.5 M NaCl)                                   23
4.2 Acidic test (0.5M H2SO4)                                  23
4.3 Sea Water test (from Penghu Island, Taiwan)               24
5 Cu NWs and graphene coated Cu NWs as electrocatalyst for HER 26

Chapter 4 Transition Metal Phosphide (Cu3P) as Electrocatalyst
1 Phosphorization of aged Cu NW after annealing               31
2 Temperature optimization of phosphorization process         32
3 Reaction time and carrier gas optimization of phosphorization
process                                                         35
4 Phosphorization at 400 °C of aged Cu NW without annealing   36
5 Chemical composition analysis                               37
6 Helical nanotube growth mechanism                           39
7 Cu3P NH @ 400 °C as electrocatalyst for HER                 41
8 Cu3P dNH @ 400 °C as electrocatalyst for HER                44
9 Behind the superior catalytic property of Cu3P NH @ 400 °C prepared
at 60 min                                                       46

Chapter 5 Transition Metal Dichalcogenide ((1T/2H) MOS2/α-MoO3) as Electrocatalyst
1 Synthesis and optimization of nanoflowers                   48
2 Identification of phases of nanoflowers                     49
3 Chemical composition and crystallinity analysis of nanoflowers  51
4 (1T/2H) MoS2/α-MoO3 as electrocatalyst for HER             55

Chapter 6 Conclusion and future perspectives                    59

References                                                      60
Appendix                                                        67

                                

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