釩酸鉍擁有適當之能隙、接近氫還原電位之導帶與高穩定，近年來常被使用於光陽極材料，而奈米結構可以減少載子所需擴散距離，本篇研究著重於釩酸鉍光陽極材料，使用兩步驟的方式合成釩酸鉍在導電玻璃(FTO)表面，第一步先用水熱法的方式合成鹵氧化鉍(BiOCl、BiOBr、 Bi4O5I2)，再由鹵氧化鉍轉變為釩酸鉍，探討由不同鹵素、改變不同條件，合成出不同表面形貌與不同覆蓋率的鹵氧化物，藉由各種分析方法，包括X光晶體繞射、電子顯微鏡、紫外光可見光光度法與電化學分析了解材料成分、表面結構、吸收率與光電流，使用Bi4O5I2經滴落塗佈法轉換而成之釩酸鉍擁有最高的表面覆蓋率，表面結構成孔洞狀，修飾Co-Bi產氧觸媒後於1.23 伏特 (vs. 可逆氫電極) 的偏壓下可以得到1.48毫安培/平方公分的光電流，表面載子傳輸效率(φ sep)也可提升至88%，載子分離效率(φ ox)也可提升至44.5%，為修飾前之4.3倍，而法拉第效率可以到達60%，最後與光陰極(氧化銅鉍)結合成二極式電化學系統；使用Bi4O5I2經陰離子交換法轉換而成之釩酸鉍為白鎢礦正方晶結構，擁有較差的光催化活性，於1.23伏特(vs. 可逆氫電極)的偏壓下只有0.26 毫安培/平方公分。

Bismuth vanadate possesses appropriate band gap, conduction band and high stability. It has been used as photoanode materials recently years. And nanostructure will reduce carrier diffusion distance. This research is focus on bismuth vanadate photoanode. Bismuth vanadate was synthesized by two step methods. First, bismuth oxyhalides (BiOCl、BiOBr、 Bi4O5I2) were synthesized on FTO by hydrothermal method. Second, transform bismuth oxyhalides into bismuth vanadate (BiVO4) by a drop casting method. Different halogens、conditions result in different morphologies and structure BiVO4. Several analytical methods were used, including X-ray diffraction、SEM、UV-vis and electrochemical measurement to analyze the ingredient, surface structure, absorption and photocurrent. BiVO4 which was converted by Bi4O5I2 through drop casting possess highest coverage ratio and porous surface structure. After photodeposition of Co-Bi oxygen evolution catalysts, BiVO4 processes 1.48 mA/cm2 photocurrent at 1.23 V (vs. RHE). Charge transfer efficiency increase to 88% which was 4.3 times higher than the bare BiVO4. Charge separation efficiency reach 53%. Faraday efficiency can reach 60% at 1.23 V (vs. RHE). In the end, connect BiVO4 photoanode and CuBi2O4 photocathode into a tandem cell. BiVO4 converted by Bi4O5I2 through anion exchange is scheelite tetragonal structure which has poor photocatalytic activity. It possesses only 0.26 mA/cm2 photocurrent at 1.23 V (vs. RHE).

目錄

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研究目的 1
1-2光電化學水分解產氫 2
第二章:文獻回顧 7
2-1 釩酸鉍的優缺點 7
2-2改質方法 8
2-2-1表面結構 (Morphology) 8
2-2-2異質接面 (Heterojunction) 9
2-2-3修飾產氧觸媒 (Oxygen evolution catalyst) 9
2-2-4摻雜 (Doping) 11
2-2-5表面電漿子共振 (Surface Plasmon Resonance) 12
2-2-6控制成長晶面 12
2-2-7氫氣、氮氣中退火 12
2-3 晶體結構與電子結構 13
2-4釩酸鉍的合成方法 15
2-4-1旋轉塗佈法 (spin coating) 15
2-4-2陰離子交換法 (anion exchange) 16
2-4-3脈衝雷射沉積 (pulsed laser deposition) 16
2-4-4滴落塗佈法 (drop casting) 16
2-5鹵氧化鉍(氯、溴、碘)合成方法 17
2-5-1氯氧化鉍 17
2-5-2溴氧化鉍 17
2-5-3碘氧化鉍 17
2-6測量與效率評估 18
2-7 重要文獻之光電流比較 21
第三章 實驗方法與步驟 22
3-1實驗藥品 22
3-2使用儀器及原理 24
3-2-1電子顯微鏡 (SEM) 24
3-2-2 X光晶體繞射 (XRD) 24
3-2-3電化學分析儀 25
3-2-4 紫外光-可見光分析儀 (UV) 27
3-2-5 儀器廠牌型號 27
3-3 實驗流程 28
3-4釩酸鉍電極合成 29
3-4-1導電玻璃清洗 29
3-4-2鹵氧化鉍合成 29
3-4-3釩酸鉍滴落塗佈法轉換 30
3-4-4 Co-Bi產氧觸媒修飾 31
3-4-5 FeOOH/NiOOH產氧觸媒修飾 31
3-4-7釩酸鉍陰離子交換法轉換 31
第四章 結果討論 32
4-1結構分析 32
4-1-1鹵氧化物結構分析 32
4-1-2滴落塗佈法之釩酸鉍結構分析 35
4-2成分分析 36
4-2-1鹵氧化鉍成分分析 36
4-2-2滴落塗佈法之釩酸鉍成分分析 38
4-3滴落塗佈法之釩酸鉍紫外-可見光吸收光譜分析 39
4-4滴落塗佈法之釩酸鉍電化學分析 40
4-5 BiVO4-CoBi/CuBi2O4-CuO-CoBi串聯 42
4-5 陰離子交換法 50
4-5-1陰離子交換法之釩酸鉍結構分析 50
4-5-2陰離子交換法之釩酸鉍成分分析 51
4-5-3陰離子交換法之釩酸鉍紫外-可見光吸收光譜分析 52
4-5-4陰離子交換法之釩酸鉍電化學分析 53
4-5-5陰離子交換法之釩酸鉍加快冷卻速度 54
第五章 結果討論 56
第六章 未來工作 57
第七章 參考文獻 58
第八章 補充資料 64

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