臺灣博碩士論文加值系統

現今社會存在著能源缺乏以及環境污染的兩大問題，有效率且無汙染地產生能源的方式相當受到關注，光電化學水分解是利用太陽光的能量進行水分解產氫產氧。本研究選用釩酸鉍作為光電極材料，於由此材料能隙小(~2.5 eV)，能有效地吸收可見光，但其缺點為電子傳導性差及與水之間的反應動力學緩慢，本實驗將利用生質柴油的副產物－甘油作為犧牲試劑的角色，以甘油氧化反應取代水氧化，以減少水分解的總耗能，並同時將甘油轉化成其他更具經濟價值的產物。
利用旋轉塗佈法將釩酸鉍沉積在FTO導電玻璃上作為光陽極，在電解液中加入甘油後能使光電流提高且起始電位前移，施加電位1.23 V vs. RHE時，在四硼酸鈉電解液中光電流密度僅有0.33 mA/cm2；而在含有2.0 M甘油的情況下可達1.28 mA/cm2，提高至3.8倍，此時電洞注入電解液的效率達140%，且利用不連續光照射下在0.7 V vs. RHE之電位觀察到甘油的存在能夠減緩電流值的衰減、改善電荷重組的情況。
在含有0.1 M甘油的四硼酸鈉溶液中施加0.7 V vs. RHE的電位，經過三小時後電流值無明顯變化，顯示電極穩定性良好，且在產物分析結果中觀察到陰極的氫氣產量與理論值相近，但光陽極沒有氧氣的生成而是偵測到二羥基丙酮及甲酸(甘油氧化之產物)，產物選擇性分別為15%及85%。

Photoelectrochemical water splitting is using solar energy to convert water into H2 and O2. By doing so, we might be potentially to solve the two major problems, i.e. energy shortage and environmental pollution, at the same time. In this study, we use BiVO4 as photoanode, which has a relatively small band gap (~2.5 eV) and thus it can absorb sun light effectively. However, it has shortcomings of poor electron conductivity and slow water oxidation kinetics. In order to boost the overall efficiency, we use glycerol, a by-product from biodiesel manufacture, as a sacrificial agent to replace water oxidation by glycerol oxidation. As a result, hydrogen can be still produced at the cathode while at the anode, glycerol is converted into other more valuable products.
BiVO4 film grown on FTO via a facile spin-coating method was employed as photoanode. The photocurrent density in the electrolyte with the introduction of glycerol is much higher than that without glycerol. The onset potential shifts towards less positive potentials as glycerol introduced. With 2.0 M glycerol in solution under 1.23 V vs. RHE, the hole injection yield of 140% is observed due to the Current Multiplication effect. The photocurrent density boosts to 1.28 mA/cm2 which is more than 3.8 times higher as that of 0.33 mA/cm2 for water oxidation.
We observed good stability for BiVO4 electrode in 0.1 M glycerol solution after 3 hrs reaction at 0.7 V vs. RHE. The product analysis results show the amount of H2 detected from cathode is close to the theoretical calculation, and the main products from glycerol oxidation are formic acid and dihydroxyacetone with the selectivity of 15% and 85%, respectively.

摘要
Abstract
目錄
圖目錄
表目錄
第一章、緒論
1.1研究動機
1.2研究方向
第2章、文獻回顧
2.1光電化學水分解
2.1.1促進電荷分離
2.1.2改善水氧化動力學
2.1.3電流倍增效應(current doubling)
2.2可再生能源
2.2.1生質柴油
2.2.2甘油氧化
第3章、實驗設備及方法
3.1實驗架構
3.2實驗藥品、設備及分析儀器
3.3.1 BiVO4光電極薄膜製備流程
3.2.2實驗藥品
3.2.3實驗材料
3.2.4實驗設備
3.2.5分析儀器
3.3儀器分析原理
3.3.1光電化學分析方法
3.3.1.1三電極系統(three electrode system)
3.3.1.2線性掃描伏安法(linear sweep voltammetry，LSV)
3.3.1.3計時安培分析法(chronoamperometry)
3.3.1.4電化學阻抗頻譜法(electrochemical impedance spectroscopy，EIS)
3.3.1.5法拉第電解定律(Faraday’s law of electrolysis)
3.3.2紫外光/可見光光譜儀 (UV-Vis spectrometer)
3.3.3場發射掃描式電子顯微鏡 (field-emission scanning electron microscope，FESEM)
3.3.4 X光繞射儀 (X-ray Diffractometer，XRD)
3.3.5 X射線光電子能譜儀(X-ray photoelectron spectroscopy，XPS)
3.3.6氣相層析儀(gas chromatograph，GC)
3.3.7高效能液相層析儀(high performance liquid chromatography，HPLC)
第4章、實驗結果與討論
4.1場發射掃描式電子顯微鏡(FE-SEM)分析
4.2 X光繞射(XRD)分析
4.3紫外光可見光分光光譜（UV-Vis）分析
4.4 BiVO4光電極之電化學分析
4.4.1甘油對光電化學表現的影響
4.4.2不同濃度甘油對電化學電阻之影響
4.4.3以甘油做為犧牲試劑之效果
4.5氣相產物分析
4.6液相產物分析
4.7 BiVO4光電極之穩定性討論
第5章、結論
第6章、參考文獻
附錄

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