臺灣博碩士論文加值系統

在本研究中，利用溶液法合成二硫化鐵奈米晶體 (FeS2 NCs)組裝在二氧化鈦 (TiO2)薄膜表面，作為近紅外光敏化劑應用於光電化學系統 (PEC)進行水分解產氫。研究中先利用溶膠凝膠法製備 TiO2/FTO，並以溶液法合成 FeS2，旋鍍於 TiO2/FTO上，形成 FeS2/TiO2/FTO異質接面光電極。
實驗中利用近紅外光雷射 (波長=808nm 強度=300mW/cm2 )照射光電極，採用 0.25M Na2S + 0.35M Na2SO3作為電解液。相較於單純 TiO2以及利用硫化鉛 (PbS)、硒化鉻 (CdSe)取代 FeS2之光電極，相較之下， FeS2/TiO2/FTO異質接面光電極對近紅外光有較佳的表現，在外電壓 0.9V vs. RHE時有最佳飽和光電流密度 6 mA/cm2 ，光電流轉換效率為0.86%，其理論產氫速率約為2.5mL/cm2-h。
最後我們呈現出以地球含量多且非毒性的FeS2結合金屬氧化物所形成的異質接面光電極，在近紅外光下有優異的光電化學產氫之表現，這在利用近紅外光能量產氫技術發展中，是相當重要的一環。

In this study, we demonstrated the sensitizer of near infrared (NIR) based on solution processable pyrite FeS2 NCs spun onto porous TiO2 films (FeS2/TiO2/FTO film) for Photoelectrochemical (PEC) hydrogen generation. Experimentally, for fabricating a FeS2/TiO2/FTO film, a TiO2/FTO substrate was first prepared by sol-gel method. Then, FeS2 NCs were spun onto TiO2/FTO substrate to form FeS2/TiO2/FTO heterojunction photoanode.
PEC cell of FeS2/TiO2/FTO film were placed in the electrolyte of 0.25M Na2S and 0.35M Na2SO3 and illuminated under NIR laser (808nm, I0=300mW/cm2). Compared with lead sulfide (PbS), cadmium selenide (CdSe) on TiO2 photoanode, FeS2/TiO2/FTO heterojunction photoanode show a better NIR photoactivity and higher saturation current density (6mA/cm2 at 0.9V vs. RHE). The conversion efficiency of photoelectrochemical cell to hydrogen was 2.64%, leading to 2.5mL/cm2-h.
In summary, we demonstrated that the earth-abundant and non-toxic FeS2 nanocrystals /metal oxides heterojunction photoanode showed an excellent performance of PEC hydrogen generation under NIR. It’s important step to further improve the overall PEC performance by absorbing light extended to NIR range.

摘要 I
Abstract II
謝誌 IV
總目錄 VI
圖表目錄 X
第一章 緒論 1
1.1 前言 1
1.2 產氫製程 6
1.3 水分解產氫 9
1.3.1 熱裂解產氫 9
1.3.2 可再生能源發電並電解水產氫 11
1.3.3 太陽能光催化及光電化學分解水產氫 13
1.4 光觸媒的介紹 16
1.5 光陽極結構與特性 21
1.5.1 二氧化鈦( TiO2，Titanium dioxide ) 21
1.5.2 二硫化鐵( FeS2 Pyrite) 25
1.6研究動機與目的 32

第二章 原理及文獻回顧 35
2-1 光電化學產氫法(Photoelectrochemical Hydrogen generation) 35
2-1-1 工作電極(Working electrode ,WE) 36
2-1-2 對電極(Counter electrode,CE) 37
2-1-3 參考電極(Reference electrode,RE) 37
2-2光電化學產氫法之原理 38
2-2-1光電化學分解水反應 39
2-2-2 PEC之能帶模擬 42
2-3 PEC中半導體電極之特性 46
2-4 光電極之PEC測量 56
2-4-1 光電流的測量(LSV) 56
2-4-2 光電轉換效率的計算(PCE) 58
2-4-3 單光光電轉換效率(IPCE) 59
2-4-4 定電流產氫測試(Chronoamperometry and hydrogen generation) 61
第三章 儀器設備與藥品 63
3-1儀器設備介紹及基本原理 63
3-1-1 高溫爐(Oven) 63
3-1-2 恆定電位儀(Potentiostat / Galvanostat) 64
3-1-3 銀/氯化銀參考電極 64
3-1-4 氙燈與單光器(Xenon lamp and Monochromator) 66
3-1-6 808nm 單光雷射 68
3-2分析儀器介紹及基本原理 69
3-2-1 X-光繞射分析儀 ( XRD ) 69
3-2.2 穿透式電子顯微鏡 (TEM ) 70
3-2-3 掃瞄式電子顯微鏡 (SEM ) 71
3-2-4 紫外光-可見光-近紅外光吸收光譜儀 (UV-Vis-NIR) 73
3-2-5 拉曼光譜儀 (Raman) 74
3-2-6 傅立葉紅外光譜儀(Fourier transform infrared spectroscopy) 75
3-3 藥品與器材 76
第四章 實驗流程 77
4-1 實驗流程架構 77
4-2 奈米晶體合成原理 78
4-3 奈米晶體合成實驗步驟 79
4-4 二氧化鈦薄膜與光陽極製作步驟 80
4-5 光陽極硫化步驟 81


第五章 實驗結果與討論 83
5-1材料特性分析 83
5-1-1 FeS2奈米晶體特性分析 83
5-1-2 二氧化鈦薄膜特性分析 86
5-2光陽極特性分析 92
5-2-1 TiO2/FeS2光陽極特性分析 92
5-2-2 TiO2/FeS2光陽極經EDT處理特性分析 97
5-2-3 TiO2/FeS2經硫化程序光陽極特性分析 101
5-3 光陽極於光電化學上的測試 108
5-3-1 電解液的配置與光源的選擇 108
5-3-2 PEC系統之配置與設定 110
5-3-3 TiO2/FeS2光陽極在PEC系統上的測試 111
5-3-4 TiO2/FeS2光陽極硫化後在PEC系統上的測試 115
5-4 不同光敏材料之PEC比較 120
5-5 光電極光電能力轉換比較 125
第六章 結論 129
第七章 未來展望 130
第八章 參考文獻 131

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