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研究生: 吳伯恩
Bo-En Wu
論文名稱: FeOx/BiVO4異質結構光化學電池與水分解之應用
Photochemical Metal Organic Deposition of FeOx Catalyst on BiVO4 for Improving Solar-Driven Water Oxidation Efficiency
指導教授: 江佳穎
Chia-Ying Chiang
口試委員: 戴龑
Yian Tai
蔡大翔
Dah-Shyang Tsai
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2017
畢業學年度: 105
語文別: 中文
論文頁數: 94
中文關鍵詞: 光電化學電池水分解光化學有機金屬沉積法
外文關鍵詞: Photoelectrochemical water splitting, photochemical metal-organic deposition, metal oxide catalyst
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使用太陽能分解水乃是一種替代能源方案的方法,而其中光電化學電池為具有非常高潛力的方法,在所有光電極材料中BiVO4光電極擁有需多光電化學電池優良的特性,例如:符合水分解所需的價帶邊界範圍、狹小的能隙、在中性電解液中具有良好的穩定性等,但BiVO4本身仍具有一項非常大的缺點需要改進,就是與水間的動力學效應非常差,因此本實驗致力於改善這項缺點。

在本實驗中選用光化學有機金屬沉積法(Photochemical metal organic deposition, PMOD),做為將金屬氧化物FeOx覆蓋於BiVO4光電極的方法,此方法不需要使用高溫、高壓及冗長的加熱時間,因此不會造成過多的能量消耗。從本實驗結過中可以發現,當覆蓋濃度太低時能夠提供的觸媒活性點相對較少,但當濃度太高時會產生光遮蔽作用,因此使用重量百分濃度為5 wt% 的iron (Ⅲ)2-ethylhexanoate製備FeOx時具有最好的效果,在施加偏壓為1.3 V vs. RHE時,光電流密度可達1.1 mA/cm2,大於原先BiVO4光電極的2.2倍,並且反應起始電位也從原先的0.65 V降到0.3 V vs. RHE,同時發現當使用PMOD法覆蓋FeOx於BiVO4光電極表面時具有保護電極表面的作用,透過計時電位法測定將反應電流固定在0.3 mA下維持2 h,其單一BiVO4光電極之電壓上升幅度約為5 wt%的iron (Ⅲ)2-ethylhexanoate塗佈所製備的FeOx/BiVO4光電極上升幅度的12倍,最後由吸收光光電子轉化效率(APCE)測試結果中得知,當入色光波長為445 nm時使用5 wt%的iron (Ⅲ)2-ethylhexanoate塗佈所製備的FeOx/BiVO4光電極其APCE效率值可達到45.5%。


Serving as a photoelectrochemical water splitting material, monoclinic BiVO4 satisfies many requirements for a highly active photoanode, such as moderate band gap (2.55eV), favorable chemical and photoelectrochemical stability, low overpotential for oxygen evolution reaction. However, it suffers from a key drawback: the slow kinetics of photon-generated charge carrier reacting with water molecules. Therefore, a layer of metal oxide oxygen evolution reaction catalyst, preparing by photochemical metal-organic deposition (PMOD), was introduced on the BiVO4 photoanode surface to enhance the efficiency of photoelectrochemical water splitting reaction.

In this study, amorphous iron oxide catalyst was deposited on the BiVO4 photoanode. It is found that there is an optimal thickness for the metal oxide catalyst due to the competition between the light sheltering effect of this catalyst layer and the amount for catalyst for reaction. With the introduction of this catalyst layer, the photocurrent density increases about two times, i.e. from 0.5 mA/cm2 for BiVO4 alone to 1.2 mA/cm2 for FeOx/BiVO4 at 1.3 V vs. RHE.

摘要 I Abstract II 致謝 III 總目錄 IV 表目錄 VII 圖目錄 VIII 第1章 緒論 1 1.1 研究動機 1 1.2 研究方向 3 第2章 文獻回顧 4 2.1 BiVO4奈米光電極製成與性質探討 7 2.2 BiVO4異質結構改質策略與原理 9 2.2.1 BiVO4半導體耦合改質(heterojunction) 10 2.2.2 BiVO4金屬離子參雜(Addition of Conductivity Dopants) 11 2.2.3 BiVO4表面添加產氧助催化劑(oxygen evolution co-catalysts) 12 2.3 光化學有機金屬沉積法 (photochemical metal-organicdeposition, PMOD)製備金屬產氧觸媒 18 第3章 實驗方法與儀器原理 21 3.1 實驗架構 21 3.2 實驗藥品、設備及分析儀器 22 3.3 FeOx/BiVO4異質結構光電極製備 23 3.3.1 BiVO4前驅液配置過程 23 3.3.2 BiVO4光電極製備過程 24 3.3.3 FeOx/BiVO4異質結構光電極製備過程 24 3.4 儀器分析原理 25 3.4.1 X光繞射儀 (X-ray Diffractometer, XRD) 26 3.4.2 X光光電子能譜儀 (X-ray Photoelectron Spectroscope, XPS) 27 3.4.3 聚焦離子束式電子顯微鏡 (Focused Ion Beam Scanning Electron Microscopy, FIB-SEM) 30 3.4.4 光電化學分析方法 31 3.4.5 紫外光/可見光光譜儀(UV/Vis Spectrometer) 33 3.4.6 入射光光電子轉化效率(incident photon-to-electron conversion efficiency, IPCE) 35 3.4.7 傅立葉紅外線光譜儀(Fourier transform infrared spectroscopy, FTIR) 36 第4章 實驗結果與討論 37 4.1 BiVO4光電極製備與分析 37 4.1.1 BiVO4光電極之掃描式電子顯微鏡(Scanning Electron Microscope, SEM)分析 37 4.1.2 BiVO4光電極拉曼(Raman)光譜分析 38 4.1.3 BiVO4光電極之X光繞射(X-ray Diffractometer, XRD)分析 39 4.1.4 BiVO4光電極之電化學分析 40 4.1.5 BiVO4光電極之紫外-可見分光光度法(Ultraviolet–visible spectroscopy,UV-Vis)分析 42 4.2 FeOx/BiVO4異質結構光電極製備與分析 45 4.2.1 FeOx/BiVO4異質結構光電極之傅立葉紅外光轉換光譜(Fourier transform infrared spectroscopy, FTIR)分析 45 4.2.2 FeOx/BiVO4異質結構光電極之掃描式電子顯微鏡(Scanning Electron Microscope, SEM)分析 46 4.2.3 FeOx/BiVO4異質結構光電極之拉曼光譜(Raman)分析 52 4.2.4 FeOx/BiVO4異質結構光電極之X光繞射(X-ray Diffractometer ,XRD)分析 53 4.2.5 FeOx/BiVO4異質結構光電極之X-ray光電子能譜儀 (X-ray Photoelectron Spectroscope, XPS)分析 54 4.2.6 FeOx/BiVO4異質結構光電極之電化學分析 59 4.3 FeOx/BiVO4異質結構中FeOx對於OER效能提升的貢獻 62 4.3.1 FeOx/BiVO4異質結構光電極與單一BiVO4光電極之水分解效率分析 63 4.3.2 FeOx/BiVO4異質結構光電極與單一BiVO4光電極入射光與吸收光光光電子轉化效率分析 68 4.4 FeOx/BiVO4異質結構光電極之穩定性分析 71 4.4.1 FeOx/BiVO4異質結構光電極之電化學穩定性分析 71 第5章 實驗結論 74 第6章 參考資料 76

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