非貴金屬奈米結構材料應用於水電解產氫｜國立臺灣科技大學博碩士論文系統

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研究生：	Tadele Hunde Wondumu Tadele Hunde Wondumu
論文名稱：	非貴金屬奈米結構材料應用於水電解產氫 Electrochemical Production of Hydrogen from Water Using Precious Metal Free Nano Structures Materials
指導教授：	王丞浩 Chen-Hao Wang
口試委員:	張仍奎 Jeng-Kuei Chang 郭俞麟 Yu-Lin Kuo 王冠文 Kuan-Wen Wang 陳燦耀 Tsan-Yao Chen
學位類別：	博士 Doctor
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	153
中文關鍵詞：	析氫反應、氧化鎢、還原氧化石墨烯、鐵摻雜、含氧空位氧化鎢、氮摻雜還原
外文關鍵詞：	Oxygen vacancies-rich, Bi-functional catalyst, Over potential
相關次數：	點閱：456 下載：0
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電解產氫觸媒中觸媒活性以及穩定性十分重要，故傳統水電解裝置通常使用鉑、鈀或銥等貴金屬作為觸媒，但會對成本支出上造成很大的壓力。有別於傳統水電解觸媒，考慮到成本、觸媒活性與穩定性，本研究使用一種具有獨特功能的多種成分組成的混合結構非貴金屬材料，用以取代貴金屬的使用。
首先，磷化氫還原鐵摻雜氧化鎢納米片/還原氧化石墨烯奈米複合物（Fe-WOxP/rGO）作為析氫反應的優良電催化劑。使用水熱法合成該電催化劑，然後用次磷酸鈉產生的膦（PH3）還原。研究觸媒反應起始電位 (onset potential)、塔弗斜率(Tafel slope)和穩定性。因此，Fe-WOxP/rGO表現出令人印象深刻的高電催化活性，在10 mAcm-2電流密度下具有54.60 mV的低過電位(overpotential)，塔弗斜率為41.99 mVdec-1和2000次線性掃描伏安曲線幾乎相同，在過電位（54.60 mV）下在0.5 M H2SO4中電解24小時依然保持穩定。 Fe-WOxP/rGO的催化活性和導電率均高於WOxP、Fe-WOxP以及WOxP/rGO。 Fe-WOxP/rGO納米複合材料的這種優異性能歸因於Fe-WOxP的奈米板狀結構中氧化鎢上的高氧空位形成與rGO納米片之間的耦合協同效應，使其成為利於析氫反應（hydrogen evolution reaction, HER）的優異觸媒。
其次，我們研究了富含氧空位之氧化鎢奈米線的催化劑，其由氮摻雜的還原氧化石墨烯（WOxNWs/N-rGO），其對酸溶液中的析氫反應（HER）具有優異的催化活性。納米線與三聚氰胺(melamine)/氧化石墨烯使用水熱法與化學氣象沉積法來合成WOxNWs/N-rGO。WOxNWs/N-rGO在10 mA cm-2的電流密度下，僅只有40 mV的過電位，其僅比Pt/C高7.01 mV，但比WOxNWs/rGO和WOxNWs低4.90和9.90 mV。WOxNWs/N-rGO的耐久性測試顯示在100 mA cm-2的大電流密度下5,000次循環後僅14 mV的過電位衰退。在55 mV的恆定過電位下，WOxNWs/N-rGO活性在12小時後也表現出約5.4％的輕微衰退。 WOxNWs/N-rGO對HER的突出表現歸因於富含氧空位的WOxNW與N-rGO之間的協同作用。
第三，我們展示了合成用於HER和OER的鈷磷硒化物納米帶（CoSe（2-X）PX NB）的三個步驟，首先使用水熱法合成CoSe2，再將95％氬氣與5％的氫氣進行退火30分鐘，最後使用化學氣相沉積法（CVD）與次磷酸鈉作為磷來源反應2小時。發現CoSe（2-X）PX NB在大範圍pH值（0-14）皆為析氫反應的優異材料。另一方面，其催化活性可以應用於氧析出反應(OER, oxygen evolution reaction)，並且電流密度為10 mA cm-2的過電位為391 mV，並且電流密度為10至40 mAcm-2 12小時長時間穩定性測試，其效能皆保持穩定。高性能，高電極穩定性和易於合成顯示CoSe（2-X）PX NB作為水電解的有效且經濟的電催化劑。
關鍵字：析氫反應、氧化鎢、還原氧化石墨烯、鐵摻雜、含氧空位氧化鎢、氮摻雜還原氧化石墨烯、電流密度、雙功能催化劑、水分解、過電位。

The production of hydrogen by electrochemical water splitting is a potential way to store energy from intermittent renewable energy sources such as solar, geothermal and wind. Synthesis and characterization of electrocatalysts for hydrogen production and oxygen evolution reaction is a great need for active, durable and cost effective materials to replace the precious metals such as platinum, iridium and ruthenium. However, the synthesis of these electrocatalysts are challenging approach to nano-materials development.
In First part of this study, we report phosphine reduced an iron-doped tungsten oxide nanoplate/reduced graphene oxide nanocomposite (Fe-WOxP/rGO) as an excellent electrocatalyst for the hydrogen evolution reaction. This electrocatalyst was synthesized using a hydrothermal method, followed by reduction with phosphine (PH3), which was generated from sodium hypophosphite. The catalyst onset potential, Tafel slope, and stability were investigated. Accordingly, Fe-WOxP/rGO exhibited impressively high electrocatalytic activity with a low overpotential of 54.60 mV, which is required to achieve a current density of 10 mAcm−2.The Tafel slope of 41.99 mVdec−1 and the linear sweep voltammetry curve is almost the same as 2,000 cycles and electrolysis under static overpotential (54.60 mV) is remain for more than 24 h in 0.5 M H2SO4. The catalytic activity and conductivity of Fe-WOxP/rGO were higher than WOXP, Fe-WOxP and WOxP/rGO. Such an outstanding performance of the Fe-WOxP/rGO nanocomposite is attributed to the coupled synergic effect between high oxygen vacancies formation on tungsten oxide in the nanoplate-like structure of Fe-WOxP and rGO nanosheet, making it as an excellent electrocatalyst for hydrogen evolution reaction.
In Second part of our work, we use the oxygen vacancy concept and further increases the amount of oxygen vacancies in WOxNWs (tungsten oxide nanowires) using heat treatment in nitrogen-rich compound such as melamine. The catalyst is composed of oxygen-vacancy-rich tungsten oxide nanowires supported by nitrogen-doped reduced graphene oxide (WOxNWs/N-rGO), which has excellent catalytic activity for the hydrogen evolution reaction (HER) in acid solution. WOxNWs/N-rGO was synthesized by solvothermally coupling tungsten oxide nanowires with melamine/graphene oxide then annealing. The WOxNWs/N-rGO exhibit only 40 mV of overpotential to afford a current density of 10 mA cm−2, which is only 7.01 mV greater than that of Pt/C but 4.90 and 9.90 mV less than those of WOxNWs/rGO and WOxNWs, respectively. A durability test of WOxNWs/N-rGO reveals only 14 mV overpotential shift after 5,000 cycles at large current density of 100 mA cm-2. At a constant overpotential of 55 mV, the WOxNWs/N-rGO activity also exhibits a slight degradation of approximately 5.4% after 12 h. The outstanding performance of the WOxNWs/N-rGO for the HER is attributed to synergetic effect between the oxygen-vacancy-rich of the WOxNWs and N-rGO.

In the third part of this study, we demonstrates a two-step, facile approach strategy for the synthesis of cobalt phosphoselenide nanobelt (CoSe(2-X)PX NB) for both HER and OER these are hydrothermal synthesis of CoSe2 followed annealing with 95%/5% of Ar/H2 for 30 minutes then reacting with sodium hypophosphite as source of phosphorus using chemical vapor deposition (CVD) methods for 2 h. The CoSe(2-X)PX NB was found to be an excellent material for the hydrogen evolution reaction over a wide pH range (0-14). On the other hand, its catalytic activity can be switched to the OER in basic media and overpotential for the OER to generate a current density of 10 mA cm-2 is 391 mV and it’s stability remain for more than 12 h at 10 to 40 mAcm-2. The high performance, prolonged electrode stability, and facile synthesis suggest that CoSe(2-X)PX NB as efficient and economic electrocatalyst for water splitting.
Key words: Hydrogen evolution reaction; tungsten oxide; reduced graphene oxide; Iron-doped, Oxygen vacancies-rich, Nitrogen-doped, Reduced graphene oxide, Current density, Bi-functional catalyst, Water splitting, and Over potential.

Table of Contents
中文摘要    iv
Abstract    vi
Acknowledgements    ix
List of Schemes    xvii
List of Tables    xvii
Chapter 1: Introduction    1
1.1.    Global energy demand    1
Chapter 2: Literature review    4
2.1.    Renewable and nonrenewable energy    4
2.2.    Advantage of hydrogen production from water    5
(c) hydrogen fuel car[18] (d) Hydrogen for space shuttle [19]    7
2.1.    Hydrogen production from renewable energy    7
2.2.    Electrochemical hydrogen production from water    8
2.3.    Graphene materials for Catalyst support    10
2.3.1.    Synthesis of reduced graphene oxide/nanostructured materials    10
2.4.    Precious metal-free Electrocatalyst for hydrogen evolution reaction    12
2.5.    Criteria for HER electrodes    14
2.5.1.    Mechanism of HER reaction    15
2.6.    Electrochemistry of the hydrogen evolution reaction (HER)    17
2.7.    Electrochemistry of the oxygen evolution reaction (OER).    18
2.8.    Parameters to evaluate the electrochemical activity of HER catalysts.    19
2.8.1.    Overpotential (ƞ)    19
2.8.2.    Tafel Slope and Exchange Current Density (j0).    19
2.8.3.    Stability    21
2.8.4.    Faradaic Eﬃciency.    22
2.9.    Factors affecting HER activity    22
2.10.    The availability of the active site    23
2.10.1.    Tungsten-based materials for hydrogen evolution reaction    23
2.10.2.    Cobalt selenide based materials for overall water splitting    33
Chapter 3: Motivation    36
3.1.    Motivation of the work    36
Chapter 4: Experimental instruments    40
4.1.    Materials characterization    41
4.2.    Electrochemical characterization    42
Chapter 5: Highly efficient and durable phosphine reduced iron-doped tungsten oxide/reduced graphene oxide nanocomposites for the hydrogen evolution reaction    44
5.1.    Introduction    44
5.2.    Experimental Section    46
5.2.1.    Synthesis of Fe-WOxP/rGO nanocomposite    46
5.3.    Results and Discussion    47
5.3.1.    The structure and morphology characterization of the Fe-WOxP/rGO nanocomposite    47
5.3.2.    Electrochemical performance measurements    54
Chapter 6: High Catalytic Activity of Oxygen-vacancy-rich Tungsten Oxide Nanowires Supported by Nitrogen-doped Reduced Graphene Oxides for Hydrogen Evolution Reaction    61
6.1.    Introduction    61
6.2.    Experimental Section    62
6.2.1.    Synthesis of WOxNWs/N-rGO    62
6.3.    Results and Discussion    64
6.3.1.    The morphology and structural characterization of  WOxNWs/N-rGO    64
6.3.2.    Electrochemical Performance Measurements    72
Chapter 7: Selenium Vacancies and Phosphorus Doping-induced Phase Transition Engineering in Cobalt Diselenide as Bifuctional Catalytic Properties for Overall Water Splitting    78
7.1.    Introduction    78
7.2.    Experimental Section    80
7.2.1.    Synthesis of CoSe(2-X)PX NB    80
7.3.    Result and discussions    81
7.4.    Electrochemical measurements    88
Chapter 8: Conclusions    95
8.1.    Highly efficient and durable phosphine reduced iron-doped tungsten oxide/reduced graphene oxide nanocomposites for the hydrogen evolution reaction (first work)    95
8.2.    High Catalytic Activity of Oxygen-vacancy-rich Tungsten Oxide Nanowires Supported by Nitrogen-doped Reduced Graphene Oxides for Hydrogen Evolution Reaction                                (Second work)    95
8.3.    Selenium Vacancies and Phosphorus Doping-induced Phase Transition Engineering in Cobalt Diselenide as Bifunctional Catalytic Properties for Overall Water Splitting                         (third work)    96
Chapter 9: Summary and out look    97
9.1.    Overall conclusion of the dissertation    97
9.2.    Outlook    98
Appendix A    101
Supporting Data for Chapter 5    101
Appendix B    107
Supporting Data for Chapter 6    107
Appendix C    117
Supporting Data for Chapter 7    117
References    120

List of Figures
Figure 1 1 World energy sources [4]    1
Figure  2 1 (a) Hydrogen fuel cell [17] (b) Pure hydrogen production from water splitting [9]    7
Figure 2 2 Sustainable pathways for hydrogen production from renewable energy, such as solar energy [9]    8
Figure 2 3 (a) Water gas shift reaction (methane reforming process) [30]  (b) Production of hydrogen by electrolysis of water [31]    9
Figure 2 4 Schematic illustration of the binding mechanisms of nanoparticles (NPs) onto rGO sheets and post immobilization (ex-situ hybridization) and in-situ binding (in situ crystallization) [35]    12
Figure 2 5 Abundance of metals in the earth’s crust that are used for constructing HER electrocatalysts [9].    13
Figure 2 6 Volcano plot of exchange current density (j0) as a function of DFT-calculated Gibbs free energy (ΔGH*) of adsorbed atomic hydrogen on pure metals [44]    15
Figure 2 7 Reaction mechanism of HER [49]    16
Figure 2 8 (i) Exfoliation of WS2 to enhance HER (ii) graphene and Nickel foam supported WS2 nanoparticles.    25
Figure 2 9 (i) Molybdenum modified tungsten phosphide, (ii) phosphorus modified tungsten nitride reduced graphene oxide nanocomposite and (iii) nitrogen doped carbon tungsten oxynitride nanowire for HER.    26
Figure 2 10 (i) molybdenum doped W18O49  and its corresponding electrochemical activity for HER, (ii) mesoporous metallic WO2 nanowire and its electrochemical activity for HER (iii) Local atomic structure modulation of tungsten trioxide and its electrochemical activities for HER.    29
Figure 4 1 Instruments for materials characterization (a) Raman spectroscopy (b) Transmision electron Microscopy (TEM) (c) X-ray diffraction (XRD) (d) X-ray photon spectroscopy (XPS)                          (e) Scanning electron microscopy (SEM)    42
Figure 4 2 (a) Electrochemical machine setup for HER (b) Solatron electrochemical workstation machine    43
Figure 5 1 (a) XRD pattern of WOxP, Fe-WOxP, WOxP/rGO, and Fe-WOxP/rGO and (b) narrow XRD scan of WOxP,Fe-WOxP,WOxP/rGO and Fe-WoxP/rGO  (c) Raman spectroscopy of WOxP, Fe-WOxP, WOxP/rGO, and Fe-WOxP/rGO (d) D  and g band of WOxP/rGO and                              Fe-WOxP/rGO.    49
Figure 5 2 SEM images of (a) WOxP, (b) Fe-WOxP, (c) WOxP/rGO, (d, e) Fe-WOxP /rGO, at different magnification, and (c, f) WOxP/rGO at different magnification.    50
Figure 5 3 (a) TEM images of Fe-WOxP/rGO, (b) HRTEM of Fe-WOxP/rGO, (c) The HAADF-STEM image for Fe-WOxP/rGO, and the corresponding EDX elemental mapping results for (d) oxygen, (e) carbon, (f) phosphorus, (g) iron and (h) tungsten.    51
Figure 5 4 (a) Full range XPS spectrum of W, O, Fe, P, and C, (b) narrow-scan O 1s, (c) narrow- Scan C 1s, (d) narrow-scan P 2p, (e) narrow-scan W 4f, and (f) narrow-scan Fe 2p.    52
Figure 5 5 XPS narrow-scan W 4f in WOxP, Fe-WOXP, WOxP/rGO, and Fe-WOxP/rGO.    54
Figure 5 6 (a) Polarization curves of WOxP,  Fe-WOxP, WOx/PrGO, Fe-WOxP/rGO,  and  Pt/C; (b) corresponding polarization curve at 10 mAcm−2,and (c) corresponding Tafel plot of WOxP, Fe-WOxP, WOxP/rGO, Fe-WOxP/rGO, and Pt/C.    55
Figure 5 7 EIS of WOxP, Fe-WOxP, WOxP/rGO, and Fe-WOxP/rGO of the indicated electrodes at η = -54.60 mV in 0.5 M H2SO4    57
Figure 5 8 (a) Polarization curves of Fe-WOxP/rGOcatalyst before and after 2,000 potential cycles and inset digital photo of the H2 bubbles formed on a Fe-WOxP/rGO and (b) Chronoamperometric response (i−t) under a static overpotential of -54.60 mV vs RHE.    59
Figure 6 1 SEM images of (a) WOxNWs, (b) WOxNWs/rGO, and (c) WOxNWs/N-rGO after the annealing at 800 °C.    65
Figure 6 2 TEM images of (a) WOxNWs/N-rGO and (b) clear crystalline fringe of WOxNWs; HAADF-STEM images of (c) WOxNWs/N-rGO and its elemental mapping of (d) carbon, (e) oxygen (f) nitrogen, and (g) tungsten.    66
Figure 6 3 XRD patterns of WOxNWs, WOxNWs/rGO, and  OxNWs/N-rGO    67
Figure 6 4 (a) Wide scan Raman spectra of WOxNWs, WOxNWs/rGO, and WOxNWs/N-rGO (b) Narrow scan Raman Spectra of WOxNWs, WOxNWs/rGO, and WOxNWs/N-rGO (c) Narrow scan Raman spectra of WOxNWs/rGO, and WOxNWs/N-rGO.    69
Figure 6 5 (a) Wide range XPS spectrum of WOxNWs/N-rGO and narrow-scan XPS of (b) W 4f, (c) N 1s, and (d) C 1s.    70
Figure 6 6 XPS narrow-scan W 4f in WOxNWs, WOxNWs/rGO, and WOxNWs/N-rGO    71
Figure 6 7 (a) Polarization curves and (b) corresponding Tafel plot of WOxNWs, WOxNWs/rGO, WOxNWs/N-rGO, and Pt/C, and (c) EIS spectra of WOxNWs, WOxNWs/rGO, and WOxNWs/N-rGO at ƞ = - 40 mV vs RHE.    75
Figure 6 8 (a) Linear sweep voltammogram (LCV) curves of WOxNWs/N-rGO after 2,000, and 5,000 potential cycles and (b) Potentiostatic response (current density versus time) under a constant potential of 55 mV.    76
Figure 7 1 SEM image of (a) as-prepared CoSe2 (b) H-CoSe2 NB  (c) CoSe(2-X)PX NB.    82
Figure 7 2 TEM image of (a) CoSe(2-X)PX NB (b) HRTEM of CoSe(2-X)PX NB (c) HAADF-STEM image for CoSe(2-X)PX NB, and the corresponding EDX elemental mapping results for (d) cobalt, (e) selenium, and (f) phosphorus.    83
Figure 7 3 XRD pattern of as-prepared CoSe2, H-CoSe2 NB, and CoSe(2-X)PX NB    84
Figure 7 4  Raman spectroscopy of (a) as-prepared CoSe2, H-CoSe2 NB and CoSe(2-X)PX NB (b) XPS narrow scan modes Co-Se of as-prepared CoSe2, H-CoSe2 NB and CoSe(2-X)PX NB (c) XPS narrow scan modes Co-Se of as-prepared CoSe2, H-CoSe2 NB and CoSe(2-X)PX NB.    85
Figure 7 5 (a) XPS wide scan range of CoSe2 as prepared, H-CoSe2 NB and H-CoSe(2-X)PX NB ( b) XPS narrow scan of Co in CoSe2, H-CoSe2 NB and H-CoSe(2-X)PX NB (c) P narrow scan in CoSe(2-X)PX NB (d) Se XPS narrow scan in CoSe2 as prepared, H-CoSe2 NB and CoSe(2-X)PX NB.    87
Figure 7 6 (a-c) HER electrocatalytic performance of Pt/C, CoSe(2-X)PX NB, H-CoSe2 NB and CoSe2 as prepared in 0.5 M H2SO4 (d-e) Tafel slope of Pt/C, CoSe(2-X)PX NB, H-CoSe2 NB and CoSe2 as  prepared in 1 M KOH.    89
Figure 7 7 (a) OER electrocatalytic performance of Pt/C, CoSe(2-X)PX NB, H-CoSe2 NB and CoSe2 as prepared (b) EIS spectra of CoSe2, H-CoSe2 NB, and CoSe(2-X)PX at ƞ = -112 mV Vs RHE in 0.5 M H2SO4 (c) Tafel slope of CoSe2, H-CoSe2 NB, Pt/C and CoSe(2-X)PX NB    91
Figure 7 8 (a) Electrochemical active surface area (EASA) of CoSe(2-X)PX NB, H-CoSe2 NB and CoSe2 CV scan of CoSe(2-X)PX NB, H-CoSe2 NB and CoSe2 at different scan rate in 0.5 M H2SO4.    92
Figure 7 9 (a) HER Stability test of CoSe(2-X)PX NB in 1 M KOH (b) HER Stability test of                          CoSe(2-X) PX NB in 1 M KOH (c) stability test for both anode and cathode in full water splitting in 1 M KOH at different current density (10 to 40 mAcm-2) each for 12 h.    93
Figure A 1 XRD Pattern of (a)WOxP,Fe-WOxP,WOxP/rGO and Fe-WoxP/rGO (b) narrow XRD scan of WOxP,Fe-WOxP,WOxP/rGO and Fe-WoxP/rGO.    102
Figure A 2 (b) XRD patterns of all samples together (i.e oxide and oxide phosphate after reduction with phosphine) (b) Raman shift of WO3,   Fe-WO3, WO3/rGO, and Fe-WO3/rGO.    102
Figure A 3 (a, c) Fe-WO3/rGO at different magnification (b, d) WO3/rGO at different magnification (e) WO3 (f) Fe-WO3    103
Figure A 4 (a) TEM images of WOxP/rGO, (b) HRTEM of WOxP/rGO, (c) The HAADF-STEM image for WOxP/rGO, and the corresponding EDX elemental mapping results for (d) oxygen, (e) carbon, (f) phosphorus, and (g) tungsten    104
Figure A 5 (a) UV-Vis spectroscopy of WO3, WOxP, Fe-WOxP, WOxP/rGO, and Fe-WOxP/rGO (b) Polarization curve of Fe-WOxP/rGO in Pt counter and graphite rode counter after 20 cycles of activation.    104
Figure A 6 SEM images of different amount of graphene oxide with 1 g of Na2WO4.2H2O precursor with (a) 10 mg GO, (b) 20 mg GO, (c) 40 mg GO (d) 80 mg GO  (e) 100 mg GO.    105
Figure A 7  (a) Polarization curves of different amount of graphene oxide with 1 g of Na2WO4.2H2O (b) Polarization curves of WOxP/rGO catalyst before and after 2,000 potential cycles.    106
Figure B 1 Cyclic Voltammetry calibration curve of SCE to RHE    107
Figure B 2 (a) SEM images of (a) untreated WOxNWs/N-rGO, (b) different heat treatment temperatures at (b) 700 oC , (c) 800 oC, and (d) 900 oC for WOxNWs/N-rGO.    108
Figure B 3 SEM images of the catalyst synthesized with glycerol for (a) WOxNWs (c) WOxNWs/rGO , and (e) WOxNWs/N-rGO, and without addition of glycerol for (b) WOxNWs, (d) WOxNWs/rGO, and (f) WOxNWs/N-rGO.    109
Figure B 4 XRD patterns of WOxNWs/N-rGO at different annealing temperatures.    110
Figure B 5 (a) Polarization curves and (b) EIS spectra of WOxNWs/N-rGO at different annealing temperatures.    110
Figure B 6 (a) The effect of melamine amount or % N for HER activity of  WOxNWs/N-rGO (b) UV-Vis spectroscopy of WOxNWs,WOxNWs/rGO, WOxNWs/N-rGO, rGO and N-rGO    111
Figure B 7 CV curves of (a) WOxNWs/N-rGO, (b) WOxNWs/rGO, and (c) WOxNWs at different scan rates; (d) current density vs. scan rates of different catalysts.    112
Figure B 8 EIS spectra of (a)WOxNWs/N-rGO, (b) WOxNWs/rGO, and (c) WOxNWs at different overpotentials.    113
Figure B 9 SEM image of WOxNWS/N-rGO (a) before and (b) after 12 h of stability test    114
Figure B 10 XRD pattern of WOxNWS/NrGO before stability test and after stability test    115
Figure B 11 (a) XPS wide-scan sprectrum of WOxNWS/NrGO after stability test (b) XPS narrow-scan spectra of tungsten in WOxNWs/N-rGO before and after stability test.    116
Figure C 1 SEM images of CoSe2 after it annealed at 400 oC for 30 minutes with 95% Ar/5% H2 followed by heat treatment at different temperature (without heat treatment, 300 oC, 400 oC and 500 oC) with Na2HPO2.2H2O for 2 h.    117
Figure C 2 XRD pattern of CoSe2 at different heat treatment with 95% Ar/5% H2 followed by heat treatment at different temperature with Na2HPO2.2H2O    118
Figure C 3 Electrochemical impendence spectroscopy (EIS) of CoSe2 as prepared, H-CoSe2 NB and CoSe(2-X)PX (a) in 0.5 M H2SO4 (b) in 1 M KOH and 1M PBS.    118
Figure C 4 (a) HER activity of different molar ratio of cobalt to Se as the treatment with 95% Ar and 5% H2 at 400 oC for 30 minutes followed by heat treatment at 400 oC with Na2HPO2.2H2O for 2 h (b) HER activities of CoSe(2-X)PX at different heat treatment with phosphine (c) HER activity of CoSe2 at different time interval heat treatment with 95% Ar /5% H2    119
List of Schemes
Scheme 6 1 Schematic illustration of synthesis of WOxNWs/N-rGO    63
Scheme 7 1 Synthesis of CoSe(2-X)PX NB    80
Scheme A 1 (a) Schematic synthesis of Fe-WO(3-X)P/rGO nanocomposite (b) photo of different composite of tungsten compound after and before reduction with phosphine.    101

List of Tables

Table 2 1 Tungsten based materials for Hydrogen evolution reaction (HER)    30
Table 4 1 List of Chemicals    40
Table 5 1 Overpotential, exchange current density, and Tafel slope data obtained from Figure 5-6 (a-c) for each catalyst.    56
Table 5 2 Electrochemical impedance fitting data from Figure 5-7 for different catalysts.    58
Table 5 3 Summary of tungsten- based materials for HER catalysts in 0.5 M H2SO4.    60
Table 6 1 The percentage of tungsten ion species obtained from XPS peak area integration.    72
Table 6 2 Summary of Tafel slope, exchange current density, and overpotential of different catalysts.    74
Table A 1 Particles size of WOxP,Fe-WOxP,WOxP/rGO and Fe-WOxP/rGO obtained from Scherer equation.    101
Table B 1 Electrochemical impedance fitting data from Figure 7c for different catalysts.    112
Table C 1 Fitting Parameters resulting from the Nyquist plots obtained from EIS results of Fig. 7b    119


                                

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全文公開日期 2024/01/07 (校內網路)
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全文公開日期 2029/01/07 (國家圖書館：臺灣博碩士論文系統)

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