氧化銅鉍(CuBi2O4)是近十年才被應用於光電化學水分解之光陰極的p型半導體，其具備小於1.8電子伏特的能隙，並且有非常正的光電流起始電位(大於可逆氫電極1伏特)，可用來作為搭配光陽極材料的理想光電化學性質。但目前實驗上尚未有可觀的光電轉換效率，限制因素尚未充分的了解，但已知的缺點可知有較短的電子傳遞距離，和電解質介面之表面反應動力及穩定性方面的侷限性，因此本研究想藉由製作具有微結構之表面形貌，減小電子傳遞之路徑與提升有效反應點位。
本實驗透過合成於氟參雜的二氧化錫(Fluorine-doped tin oxide,FTO)上具有片狀微結構之碘氧化鉍(Bi4O5I2)，以滴落塗佈法法(drop casting)給予銅元素並進行高溫退火，將碘氧化鉍轉換為實驗的目標產物氧化銅鉍，並分別以退火溫度、滴液量來調整實驗的合成過程，藉由掃描式電子顯微鏡了解退火溫度對於合成後的表面結構影響，並透過X-光繞射分析了解各式合成條件搭配下，合成目標產物氧化銅鉍的結果，來尋找到較合適的合成條件。並對各式合成條件下的試片進行線性伏安法的電化學分析，初步了解不同合成條件對於產品的電化學影響，並且比較在有無電子犧牲試劑的電化學系統中的光電流表現，發現在具有電子犧牲的影響下，所量測電位窗範圍內的光電流皆大於不含電子犧牲試劑系統數倍之多，這些實驗結果表示材料表面與電解質的介面具有相當程度的電子傳遞障礙，這引導實驗進行後續表面觸媒修飾的動機，並且在實驗中透過紫外光-可見光之漫反射分析與莫特-蕭特基圖，觀察到氧化銅鉍的能隙與能帶分佈。表面修飾部分則進行二氧化鈦的修飾作為保護層，並以鉑及鈷化合物作為產氫觸媒，最終將與光陽極釩酸鉍結合為二極式電化學系統。

Copper bismuth oxide (CuBi2O4) is a p-type semiconductor which band gap is less than 1.8 eV, and the onset potential is positive than 1 V vs. RHE. These good properties make it a promising photocathode material for solar water splitting. However, short charge carrier transport distance, poor surface reaction kinetic and stability limit the efficiency of CuBi2O4.
The synthesis of CuBi2O4 is by drop-casting/heating methods on nanosheet structured Bi4O5I2 electrode. The synthesis procedures were adjusted by changing the annealing temperature and drop casting volumes of solution. The surface morphology differences were characterized by SEM (Scanning electron microscope) measurements, where the compositions of CuBi2O4 were confirmed by XRD (X-ray Diffraction) analysis. The photocurrents were quantified with LSV (Linear Sweep Voltammetry) measurement. There is a four times difference for photocurrent at 0.4 V vs RHE (Reversible Hydrogen Electrode) with and without sacrificial agent. These properties indicate that there are some barriers between electrolyte and bulk material. Band structure were characterized with UV–vis diffuse reflectance and Mott-Schottky plot. Band gap is about 1.8 eV and flat band is at 1.4 V vs RHE. Decorate TiO2 as protection layer and afterward electrodeposition of Pt or Co-Bi as hydrogen evolution catalyst. In the end, connect BiVO4 photoanode and CuBi2O4 photocathode into a tandem cell.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目錄 v
圖目錄 viii
表目錄 xi
第一章 前言 1
1.1 研究背景 1
1.2 研究動機與目的 2
1.3 論文架構 3
第二章 文獻回顧 4
2.1半導體 4
2.1.1 能隙(Band gap) 4
2.1.2費米能階(Fermi level) 6
2.1.3 p型與n型半導體 7
2.1.4 能帶彎曲(Band bending) 8
2.2 太陽能應用 9
2.2.1 光電化學水分解(Photoelectrochemical water splitting) 10
2.2.2 光電轉化效率13 14
2.3材料介紹 15
2.3.1 CuBi2O4材料性質 15
2.3.2 Bi4O5I2材料性質 18
2.4 改質方法 18
2.4.1 表面微結構(microstructure) 18
2.4.2 異質接面(heterojunction) 19
2.4.3 修飾產氫觸媒 20
第三章 實驗方法 21
3.1 實驗流程 21
3.2 實驗藥品與工具 23
3.3 試片製備 24
3.3.1 基板前處理 24
3.3.2 建構表面微結構 25
3.3.3 表面材料轉換 25
3.3.4 表面修飾TiO2 26
3.3.5 修飾產氫觸媒 26
3.4 模擬光電化學水分解系統實驗介紹 27
3.4.1 光源光譜組成 27
3.4.2 三極式電化學系統 29
3.4.3 線性掃描伏安法(Linear Sweep Voltammetry, LSV) 29
3.5 分析方法 30
3.5.1 掃描式電子顯微鏡(Scanning electron microscope, SEM) 30
3.5.2 能量散佈光譜儀(Energy Dispersive Spectrometer, EDS) 31
3.5.3 X射線繞射分析(X-ray Diffraction, XRD) 32
3.5.4 紫外線-可見光漫反射光譜(UV-Vis Diffuse Reflectance Spectra) 33
3.5.5 氣相層析儀 33
第四章 實驗分析與結果 34
4.1 Bi4O5I2合成結果與分析 34
4.2 CuBi2O4合成實驗結果與分析 37
4.2.1 表面形貌分析 38
4.2.2 X-ray繞射分析 39
4.2.3 LSV電化學分析 42
4.2.4 CuBi2O4 Band structure分析 47
4.2.5 CuBi2O4之載子相關效率 50
4.3 CuBi2O4表面修飾 52
4.3.1 表面修飾TiO2 52
4.3.2 產氫觸媒修飾 53
4.3.3 異質接面 58
4.4 CuBi2O4與BiVO4之二極式系統 59
第五章 總結與未來工作 64
5.1 實驗總結 64
5.2 未來工作 65
參考文獻 66
補充資料 71

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