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研究生： 邱泓鈞
Chiu, Hung-Chun
論文名稱： 高效能鐵-鈣氧化物中性環境水氧化觸媒之開發
Iron-calcium Oxide as an Efficient Catalyst for Electrocatalytic Oxygen Evolution under Neutral Conditions
指導教授： 林家裕
Lin, Chia-Yu
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2017
畢業學年度： 105
語文別： 英文
論文頁數： 69
中文關鍵詞： 鈣鐵氧化物 、鉍釩氧化物 、水氧化 、光電化學水分解
外文關鍵詞： Bismuth vanadate, Calcium iron oxide, Oxygen evolution, Photoelectrochemical water splitting
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    • 本研究成功合成不同鈣含量之鐵-鈣氧化物薄膜，並對其在中性環境下之電催化水氧化性能做全面性地探討。鐵-鈣氧化物之晶相、化學組成以及電催化性能係藉由X光繞射、拉曼光譜、感應耦合電漿質譜、循環伏安法、線性掃描伏安法和定電流電解等技術與實驗進行分析。研究發現未摻入鈣所得之薄膜具有磁赤鐵礦的結晶相，且對於磷酸根離子並無明顯的反應性；但摻入鈣而合成之薄膜，由於失去了長程序化之特性而在表面展現出對於磷酸根離子之高反應性。無論施加電流密度與否，磷酸鹽的存在造成鐵-鈣氧化物表面的鈣析出並且在薄膜表面形成具電活性之磷酸鐵。鐵-鈣氧化物之塔弗斜率和交換電流密度都會隨著摻入鈣濃度的上升而上升，意味著鈣的摻入不只改變了水氧化反應的機制也增強了其電催化水氧化之活性。當摻入最佳化的鈣濃度之後，所製備之鐵-鈣氧化物薄膜的電活性更勝於至今於中性環境下有著最優異性能的氧化鈷水氧化觸媒。以最佳化條件所製備之鈣-鐵氧化物薄膜於1.0 M酸鹼值7的磷酸鹽緩衝溶液中，僅需過電位0.65伏特來維持10毫安培電流密度或者0.12 s-1轉換速率。當鐵-鈣氧化物修飾於鉍釩氧化物光陽極時，不僅其表面水氧化反應電洞傳遞之動力有顯著之提高，其光電催化水氧化之光電流和光穩定性也大為提升。

    Iron-calcium oxide (CaFeOx) thin film with tunable calcium contents were synthesized, and their electrocatalytic properties towards the oxygen evolution reaction (OER) in neutral aqueous conditions were investigated. Crystal phase, chemical composition, and electrocatalytic properties of the synthesized CaFeOx thin films were characterized using X-ray diffraction, Raman spectroscopy, inductively coupled plasma mass spectrometry, cyclic voltammetry, linear sweep voltammetry, and controlled-current electrolysis. It was found that the prepared thin film without the incorporation of calcium has -Fe2O3 crystalline phase and exhibits minimal reactivity to phosphate, but those with the incorporation of calcium losses their long-range order and displays high surface reactivity to phosphate ions to form redox-active iron phosphate on their surface. The leaching of surface calcium in CaFeOx occurred in presence of phosphate regardless of applied current density. In addition, Tafel slope along with exchange current density of CaFeOx thin films increased with increasing calcium, suggesting the incorporation of calcium modifies OER mechanism and enhances electrocatalytic activity of CaFeOx thin film. With optimal calcium content, the activity and stability of CaFeOx outperformed those of CoPi, a state-of-art Earth-abundant material based OER catalyst in neutral aqueous media reported to date, under high turnover conditions. An overpotential of 0.65 V was required for CaFeOx to maintain a current density of 10 mA cm-2 (or a turnover frequency of 0.12 s-1) in 1.0 M phosphate buffer (pH 7). When being integrated onto the BiVO4 photoanode, CaFeOx facilitated the kinetics of OER and interfacial hole transfer, resulting in remarkable enhancement in photocurrent response and photostability of the BiVO4 photoanode.

    中文摘要 I Abstract II Acknowledgement III Table of Content IV List of Tables VI List of Figures VII Chapter 1 Introduction 1 1.1 Background 1 1.2 Catalysts for oxygen evolution reaction (OER) 3 1.2.1 Noble-metal oxides based OER catalysts 6 1.2.2 Transition metal oxides/hydroxides based OER catalyst 8 1.2.3 Other OER catalysts 11 1.3 Mechanism of OER 15 1.4 Motivation and scope of the dissertation 22 Chapter 2 Experimental 25 2.1 Materials 25 2.2 Instrumentation 28 2.3 Electrode preparation 29 2.3.1 Fabrication of Fe2O3 thin film modified electrodes (FTO|Fe2O3) 30 2.3.2 Fabrication of CaFeOx thin film modified electrodes (FTO|CaFeOx) 30 2.3.3 Fabrication of FTO|Co-Pi 30 2.3.4 Fabrication of FTO|FeOx 31 2.3.5 Fabrication of FTO|IrO2 31 2.3.6 Fabrication of pristine and CaFeOx modified BiVO4 photoanodes 32 2.4 Physical characterization 33 2.5 Electrochemical characterization 34 2.6 O2 measurement 36 Chapter 3 Results and Discussions 37 3.1 Physical characterization 37 3.1.1 X-ray diffraction patterns and SEM images 37 3.1.2 XPS spectra 39 3.2 Electrocatalytic properties of FTO|CaFeOx 41 3.2.1 Tafel slope and the initial overpotential () 41 3.2.2 Comparison with state-of-art OER catalyst 44 3.2.3 Investigation of activity under different pH and atmospheres 48 3.2.4 Comparison with the most active OEC “IrO2” 51 3.3 Mechanistic interpretation 52 3.4 Application in photoelectrochemical water splitting 56 Chapter 4 Conclusion and Suggestion 60 4.1 Conclusion 60 4.2 Suggestion and Outlook 61 4.2.1 Enhancement in PEC performance of nanoWO3 phtoanode via pretreatment and CaFeOx modification 61 References 62 Appendix 68

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