BiVO4為基底的光陽極應用在選擇性氧化HMF及其衍生物

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姓名

趙冠傑(Guan-Jie Zhao) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

BiVO4為基底的光陽極應用在選擇性氧化HMF及其衍生物
(Photoelectrochemical selective oxidation of HMF derivatives on BiVO4-based photoanode)

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至系統瀏覽論文 (2025-8-17以後開放)

摘要(中)

光電化學系統（PEC）可以像自然界通過光合作用一樣直接利用半導體
電極中的光生電子-電動對來催化反應，若使用生物質當反應物進行選擇性氧化來生成高經濟價值的產物，將是一道對環境友善且節省能源的製程。我們究嘗試開發吸收可見光的光陽極，並應用在 5- 羥甲基糠醛 (5-hydroxymethylfurfural, HMF)的選擇性氧化上。本研究首先用旋轉塗佈法製備 BiVO4 薄膜光電極，並經由塗佈緩衝層、保護層和裝載共觸媒來提升光電極之性能。緩衝層改善了 BiVO4 表面的性質，使晶粒更為均一完整，在1.2 V vs. RHE 下，光電流密度提升 33%，且 IPCE 在波段 400 nm 時從 16%提升至 34%；NiOx 共觸媒的裝載提升了氧化動力，讓水解反應之起始電位往還原方向 0.2 V vs. RHE，但在高偏壓區的電流卻出現被抑制的情形，代表也存在界面與表面的問題需要克服；保護層 TiO2 的性質有類似透明導電氧化物(Transparent conductive oxide)的作用，能有效降低半導體與電解液界面之電子-電洞對再結合。而後我們選用光電流密度最高的 BiVO4/SnO2光電極在不同離子電解液與 pH 值環境下測試穩定性，發現在 pH=10 的硼酸鈉緩衝溶液有最好的表現性，並在此進行 HMF 之選擇性氧化反應。我們藉由 TEMPO 當反應媒介，成功轉化出產物 FDCA，在反應總載子數為 78 庫倫後，HMF 有 74%的轉化率，FFCA 與 FDCA 分別有 29%、30%的產率，40%、41%的選擇率，法拉第效率為 91%。而由濃度變化的計算，我們得出 HMF 為一級反應。

摘要(英)

The photoelectrochemical (PEC) can directly utilize the photo-generatedelectron-hole pair in semiconductor electrode to catalyze the reaction like nature
through photosynthesis. If the biomass is used as the reactant for selectiveoxidation to generate a product of high economic value, it will be anenvironmentally friendly and energy-saving process. We tried to develop a
photoanode that absorbs visible light and applies it to the selective oxidation of 5-hydroxymethylfurfural (HMF). In this study, the BiVO4 thin film photoelectrode
was first prepared by spin coating, and the performance of the photoelectrode was
improved by coating a buffer layer, a protective layer, and a co-catalyst. The buffer
layer improves the properties of the BiVO4 structure, making the grain moreuniform and complete. At 1.2 V vs. RHE, the photocurrent is increased by 33%,and the IPCE is increased from 16% to 34% at 400 nm. Loading of the NiOx cocatalyst improves the oxidation kinetics, shifting the oneset potential to thenegative side by 0.2 V vs. RHE of the water splitting reaction, but the current in
the high-bias region is suppressed, indicating that there are also problems with theinterface and surface. The property of the protective layer TiO2 is similar to that
of a transparent conductive oxide (TCO), which can effectively reduce the
recombination of electron-hole pairs at the interface between the semiconductorand the electrolyte.
After that, we selected the BiVO4/SnO2 photoelectrode with the highestphotocurrent properties to test the stability under different electrolytes and pH
environments, and found that the borate buffer solution at pH=10 showed the best performance.
By using TEMPO as the mediator, we have demonstrated a electrochemicaloxidation of HMF into FDCA. When 78 C was passed, HMF had a conversion
rate of 74%, FFCA and FDCA had 29%, 30% yield, and 40%, 41% selectivity,Faraday efficiency is 91%. From the calculation of the concentration change, we
conclude that HMF is a first order reaction.

關鍵字(中)

★ 光陽極
★ 選擇性氧化
★ 5-羥甲基糠醛

關鍵字(英)

★ BiVO4
★ selectove oxidation
★ HMF

論文目次

目錄
摘要................................................................................................................i
Abstract .........................................................................................................ii
誌謝..............................................................................................................iv
目錄............................................................................................................... v
圖目錄........................................................................................................viii
表目錄.........................................................................................................xii
第一章、緒論 ........................................................................................... 1
1-1 前言................................................................................................. 1
1-2 光觸媒發展 .................................................................................... 3
1-3 研究動機......................................................................................... 5
第二章、文獻回顧 ................................................................................... 7
2-1 半導體光觸媒 ................................................................................ 7
2-1-1 半導體................................................................................. 7
2-1-2 光觸媒................................................................................. 9
2-1-3 半導體與電解液界面........................................................ 9
2-2 光電化學分解水 .......................................................................... 11
2-3 光電效率....................................................................................... 12
2-4 BiVO4半導體光觸媒................................................................... 13
2-4-1 BiVO4性質........................................................................ 13
2-4-2 BiVO4優缺點.................................................................... 14
2-4-3 BiVO4改善方法................................................................ 16
2-4-3-1 表面型態控制....................................................... 16
vi
2-4-3-2 微量元素摻雜....................................................... 16
2-4-3-3 鈍化層................................................................... 17
2-4-3-4 共觸媒................................................................... 18
2-4-3-5 緩衝層................................................................... 19
2-5 電解液對 BiVO4的影響............................................................. 21
2-6 光催生質物與選擇性氧化 ......................................................... 22
2-6-1 光催化生質物.................................................................. 22
2-6-2 選擇性氧化...................................................................... 22
第三章、研究方法 ................................................................................. 25
3-1 實驗藥品 ..................................................................................... 25
3-2 實驗儀器 ..................................................................................... 28
3-3 實驗步驟 ..................................................................................... 30
3-3-1 光電極製備...................................................................... 30
3-3-1-1 BiVO4 電極........................................................... 30
3-3-1-2 BiVO4/SnO2 電極 ................................................. 31
3-3-1-3 TiO2/BiVO4/SnO2 電極......................................... 31
3-3-1-4 NiOx/BiVO4/SnO2 電極........................................ 31
3-3-1-5 NiOx/TiO2/BiVO4/SnO2 電極................................ 32
3-3-2 光電化學測量.................................................................. 32
3-3-3 選擇性氧化之電解液....................................................... 33
3-3-4 選擇性氧化....................................................................... 33
3-3-4-1 反應系統............................................................... 33
3-3-4-2 液相層析分析....................................................... 34
第四章、結果與討論 ............................................................................. 35
vii
4-1 BiVO4光電極............................................................................... 36
4-1-1 基本性質分析................................................................... 36
4-1-2 電化學分析....................................................................... 41
4-1-3 光電效率探討.................................................................. 43
4-2 BiVO4/SnO2 光電極.................................................................... 46
4-2-1 基本性質分析................................................................... 46
4-2-2 電化學分析....................................................................... 48
4-3 NiOx/ BiVO4/SnO2 光電極.......................................................... 51
4-3-1 基本性質分析................................................................... 51
4-3-2 電化學分析....................................................................... 54
4-4 TiO2/ BiVO4/SnO2 光電極 .......................................................... 58
4-4-1 基本性質分析................................................................... 58
4-4-2 電化學分析....................................................................... 60
4-5 NiOx/TiO2/ BiVO4/SnO2 光電極................................................. 63
4-5-1 電化學分析...................................................................... 63
4-6 最適化反應環境 .......................................................................... 66
4-7 選擇性氧化 .................................................................................. 70
第五章、結論 ......................................................................................... 75
5-1 結論............................................................................................... 75
5-2 未來展望 ..................................................................................... 76
參考文獻..................................................................................................... 77
附錄............................................................................................................. 83

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指導教授

李岱洲(Tai-Chou Lee)

審核日期

2020-8-18

推文